Curable resin composition for use in water-based coating materials

ABSTRACT

The present invention relates to a curable resin composition for use in water-based coating materials which includes as essential components an emulsion polymer (A) containing tertiary amino groups obtained by carrying out emulsion polymerization of a vinyl monomer containing a tertiary amino group with another copolymerizable vinyl monomer in a water-based medium, and a compound (B) containing, at least, an epoxy group and a hydrolyzable silyl group, with this composition preferably also including a water-based compound (C) obtained by adding a neutralizing agent to a vinyl polymer (I) containing acidic groups and/or tertiary amino groups so as to neutralize at least 10% of the acidic groups and/or the tertiary amino groups, and then dispersing or dissolving in water, and/or a compound (D), which is not included in compound (B), and contains hydrolyzable silyl group and/or a silanol group. The coating material provided by the composition of the present invention is curable at ambient temperatures and demonstrates excellent coating properties. Moreover, the cured coating obtained from the composition of the present invention offers superior resistance to weathering, solvents, chemicals and water, and is not problematic with respect to conservation of the environment.

TECHNICAL FIELD

The present invention relates to a novel and useful curable resincomposition for use in water-based coating materials, and morespecifically, to a curable resin composition for use in a water-basedcomposition which includes as coat-forming components at least anemulsion polymer containing a specific tertiary amino group and acompound having an epoxy group and a hydrolyzable silyl group. Thiscurable resin composition for use in water-based coating materials isnot only superior with respect to its workability and curing properties,but also provides a cured coating with excellent resistance toweathering, solvents, chemicals, and water. Accordingly, thiscomposition is particularly useful when applied in coating materials.

BACKGROUND ART

Fueled by such demands worldwide as protection of the environment and animprovement in workplace conditions in recent years, it has becomenecessary to move away from conventional coating materials containingorganic solvents, to coating materials which release little organicsolvent into the atmosphere. In addition, from the perspective of energyconservation, as well, the development of a type of coating resin whichform crosslinking at ordinary temperature has been particularlyattractive.

A composition of a water-based emulsion composition consisting of acopolymer composed of an unsaturated monomer of the ethylene family andan aminoalkyl(meth)acrylate having a primary or secondary amino group,and a epoxy silane coupling agent has been proposed heretofore (JapanesePatent Application, First Publication No. Sho 61-28543). However, thecured coating obtained from this composition has been problematic inthat it tends to be inferior with respect to its weather resistantproperties and the like.

Accordingly, the present inventors began extensive research aimed atdeveloping a composition which would resolve the aforementioned problemsencountered in the conventional art, while also meeting the variousdemands of the coating industry as described above.

Therefore, the present invention has as an objective for the provisionof a curable resin composition for use in water-based coating materialswhich is novel and has an extremely high degree of utility, thecomposition having excellent workability and curing properties, whilecontaining little or no organic solvent as compared to conventionalorganic solvent-based coatings, and moreover, offering a cured coatingwhich is superior with respect to resistance to weathering, solvents,chemicals and water.

Additionally, in view of energy conservation, it is also an objective ofthe present invention to provide a novel curable resin composition foruse in water-based coating materials with a high degree of utility,which can form crosslinking at ordinary temperature.

DISCLOSURE OF INVENTION

As a result of exhaustive research to resolve the above-describedproblems, the present inventors completed the present invention upon thediscovery that a composition comprising an emulsion polymer (A)containing tertiary amino groups which is obtained by carrying outemulsion polymerization of a vinyl monomer containing a tertiary aminogroup and another copolymerizable vinyl monomer in a water-based medium,and a compound (B) containing, at least, an epoxy group and ahydrolyzable silyl group, has superior coating properties and provides acured coating with excellent resistance to weathering, yellowing fromheat, solvents, chemicals, dirt shedding, and water, while enabling areduction in the amount of organic solvent contained therein.

Accordingly, the first objective of the present invention is theprovision of a curable resin composition for use in water-based coatingmaterials, characterized in including an emulsion polymer (A) containingtertiary amino groups which is obtained by carrying out emulsionpolymerization of a vinyl monomer containing a tertiary amino group andanother copolymerizable vinyl monomer in a water-based medium, and acompound (B) containing, at least, an epoxy group and a hydrolyzablesilyl group.

Another objective of the present invention is the provision of a curableresin composition for use in water-based coating materials,characterized in including an emulsion polymer (A) containing tertiaryamino groups which is obtained by carrying out emulsion polymerizationof a vinyl monomer containing a tertiary amino group and anothercopolymerizable vinyl monomer in a water-based medium; a water-basedcompound (C) which is obtained by adding a neutralizing agent to a vinylpolymer (I) containing acidic groups and/or tertiary amino groups, so asto neutralize at least 10% of the aforementioned acidic groups and/ortertiary amino groups, and then dispersing or dissolving in water; and acompound (B) containing, at least, an epoxy group and a hydrolyzablesilyl group.

Another objective of the present invention is the provision of a curableresin composition for use in water-based coating materials,characterized in including an emulsion polymer (A) containing tertiaryamino groups which is obtained by carrying out emulsion polymerizationof a vinyl monomer containing a tertiary amino group and anothercopolymerizable vinyl monomer in a water-based medium; a compound (B)containing, at least, an epoxy group and a hydrolyzable silyl group; anda compound (D), which is not included in compound (B), and contains ahydrolyzable silyl group and/or silanol group.

Another objective of the present invention is the provision of a curableresin composition for use in water-based coating materials,characterized in including an emulsion polymer (A) containing tertiaryamino groups which is obtained by emulsion polymerizing a vinyl monomercontaining a tertiary amino group and another copolymerizable vinylmonomer in a water-based medium; a water-based compound (C) which isobtained by adding a neutralizing agent to a vinyl polymer (I)containing acidic groups and/or tertiary amino groups, so as toneutralize at least 10% of the aforementioned acidic groups and/ortertiary amino groups, and then dispersing or dissolving in water; acompound (B) containing, at least, an epoxy group and a hydrolyzablesilyl group; and a compound (D), which is different from compound (B),and contains a hydrolyzable silyl group and/or silanol group.

In the curable resin composition for use in a water-based coatingmaterial according to the present invention, it is preferable thatemulsion polymer (A) containing tertiary amino groups also have acarboxyl group.

Additionally, it is preferable that emulsion polymer (A) containingtertiary amino groups be prepared using at least a vinyl monomercontaining a hydroxyl group as the monomer component.

It is also preferable that emulsion polymer (A) containing tertiaryamino groups be prepared using at least a vinyl monomer containing acycloalkyl group as the monomer component.

It is also preferable that emulsion polymer (A) containing tertiaryamino groups be prepared using a soap-free polymerization method.

It is also preferable that emulsion polymer (A) containing tertiaryamino groups be neutralized with an acidic compound, so that the ratioof the equivalent weight of the acidic compound with respect to that ofthe tertiary amino groups included in emulsion polymer (A) be 0.1 ormore.

It is also preferable that emulsion polymer (A) containing tertiaryamino groups be neutralized with a basic compound, so that the ratio ofthe equivalent weight of the basic groups in the basic compound withrespect to that of the acidic groups included in emulsion polymer (A) be0.1 or more.

It is also preferable that emulsion polymer (A) containing tertiaryamino groups be an acrylic polymer.

In the curable resin composition for use in water-based coatingmaterials according to the present invention, it is preferable that thevinyl polymer (I) containing acidic groups and/or tertiary amino groupsbe prepared using at least a vinyl monomer containing a hydroxyl groupas a starting component.

It is also preferable that the vinyl polymer (I) containing acidicgroups and/or tertiary amino groups be prepared using at least a vinylmonomer containing a cycloalkyl group as a starting component.

It is also preferable that the vinyl polymer (I) containing acidicgroups and/or tertiary amino groups be a combination of an acrylicpolymer and a fluoro olefin polymer.

It is also preferable that the vinyl polymer (I) containing acidicgroups and/or tertiary amino groups be either an acrylic polymer or afluoro olefin polymer.

The present invention's curable resin composition for use in water-basedcoating materials fundamentally contains an emulsion polymer (A)containing tertiary amino groups which is obtained by carrying outemulsion polymerization of a vinyl monomer containing a tertiary aminogroup and another copolymerizable vinyl monomer in a water-based medium;and a compound (B) containing, at least, an epoxy group and ahydrolyzable silyl group.

In general, when compound (B) containing, at least, an epoxy group and ahydrolyzable silyl group is mixed with an emulsion polymer, thehydrolyzable silyl groups in compound (B) undergo hydrolysis over ashort period of time, followed by a condensation reaction, leading toconsumption of the hydrolyzable silyl groups, or consumption of theepoxy groups in compound (B) by a ring opening reaction with water.Accordingly, it was anticipated that this mixture would show inferiorcuring, and give rise to a coating having a number of inferiorproperties.

It thus came as a surprise to discover that the present invention'scurable resin composition for use in water-based coating materialscontaining as the emulsion polymer, a emulsion polymer (A) containingtertiary amino groups obtained by carrying out emulsion polymerizationof a vinyl monomer containing a tertiary amino group and anothercopolymerizable vinyl monomer in a water-based medium, has excellentcuring properties despite the inclusion of compound (B). Moreover, eventhough the curable resin composition for use in water-based coatingmaterials according to the present invention includes little or noorganic solvent as compared to conventional organic solvent-typecompositions, it provides a coating of remarkably superior properties.

In addition, it was found that the combination of emulsion polymer (A),water-based compound (C) which is obtained by adding a neutralizingagent to a vinyl polymer (I) containing acidic groups and/or tertiaryamino groups, so as to neutralize at least 10% of the aforementionedacidic groups and/or tertiary amino groups, and then dispersing ordissolving in water, and compound (B), in the present invention'scurable resin composition for use in water-based coating materials notonly provides a coating having excellent properties and capabilities,but also realizes improved flow characteristics so that coat formationis improved. Moreover, this combination also results in improvedsmoothness, leading to a better gloss of film surface, and reducessagging, which can become a problem when applying to vertical surfaces.In addition, it is also possible to control orientation of aluminum inthe case of a metallic coating which is obtained by adding aluminumpaste. Thus, the coating operation is markedly improved, while thefinished appearance of the coating is excellent.

In addition, it was understood that a curable resin composition for usein water-based coating materials according to the present inventionwhich includes emulsion polymer (A), compound (B) containing, at least,an epoxy group and a hydrolyzable silyl group, and, additionally, acompound (D), which is not including in compound (B), and contains ahydrolyzable silyl group and/or silanol group, provides a cured coatingwith excellent resistance to weathering, solvents, chemicals, dirtshedding, and water.

Further, it was found that a curable resin composition for use inwater-based coating materials according to the present invention whichincludes emulsion polymer (A), compound (B), water-based compound (C),and compound (D), has excellent curability, and superior coatingproperties despite the inclusion of little or no organic solvent, aswell as improved flow characteristics and ease of coating operation.Moreover, the coating obtained from this composition demonstrates animproved finished appearance, and superior resistance to weathering,solvents, chemicals, staining, and water. Accordingly, this coatingcomposition has an extremely high degree of utility.

BEST MODE FOR CARRYING OUT THE INVENTION

Accordingly, one preferred embodiment of the present invention is acurable resin composition for use in water-based coating materials whichincludes an emulsion polymer (A) containing tertiary amino groups whichis obtained by carrying out emulsion polymerization of a vinyl monomercontaining a tertiary amino group and another copolymerizable vinylmonomer in a water-based medium; a water-based compound (C) which isobtained by adding a neutralizing agent to a vinyl polymer (I)containing acidic groups and/or tertiary amino groups, so as toneutralize at least 10% of the aforementioned acidic groups and/or aminogroups, and then dispersing or dissolving in water; a compound (B)containing, at least, an epoxy group and a hydrolyzable silyl group; anda compound (D), which is not including compound (B), and contains ahydrolyzable silyl group and/or silanol group.

In addition to a curable resin composition for use in water-basedcoating materials according to the present invention which includesemulsion polymer (A), compound (B), water-based compound (C), andcompound (D), all other variations of the present invention are ofcourse novel and of sufficient utility, provided that they contain atleast emulsion polymer (A) and compound (B) as essential components.

The present invention's curable resin composition for use in water-basedcoating materials contains as an essential coat-forming componentemulsion polymer (A) containing a tertiary amino group which is obtainedby carrying out emulsion polymerization of a vinyl monomer containing atertiary amino group and another copolymerizable vinylmonomerin awater-based medium. As examples of emulsion polymer (A), variousso-called vinyl polymers may be mentioned, including acrylic polymers,aromatic vinyl polymers, vinyl ester polymers and the like. Of these,acrylic emulsion polymers are preferred in particular.

Particularly suitable examples of the tertiary amino vinyl monomer(hereinafter abbreviated as (a-1)) used when prepared emulsion polymer(A) include the various (meth)acrylic acid ester monomers such as2-dimethylaminoethyl(meth)acrylate, 2-diethylaminoethyl(meth)acrylate,3-dimethylaminopropyl (meth)acrylate, 3-diethylaminopropyl(meth)acrylate, 3-dimethylaminopropyl acrylamide,N-(2-(meth)acryloyloxyethyl)piperidine, N-(2-(meth)acryloyloxyethyl)pyrrolidine and N-(2-(meth)acryloyloxyethyl)morpholine; the variousaromatic monomers such as 4-(N,N-dimethylamino)styrene,4-(N,N-diethylamino)styrene and 4-vinylpyridine; the various vinylethers having a tertiary amino group such as2-dimethylaminoethylvinylether, 2-diethylaminoethylvinylether,4-dimethylaminobutylvinylether, 4-diethylaminobutylvinylether and6-dimethylaminohexylvinylether.

Particularly representative examples of the other vinyl monomer(hereafter ahbreviated as (a-2) ) to he copolymerized with the tertiaryamino vinyl monomer (a-1) mentioned above include the variouspolymerizable monomers such as alkyl(meth)acrylates, alkyl crotonates,dialkylesters of unsaturated dibasic acids, monocarboxylic acid vinylesters, and aromatic vinyl monomers; various monomers having one or morehalogen atoms, such as a fluorine or chlorine, per molecule; variousmonomers having a non-functional silicon atom such as monomers havingpolysiloxane bonds; various monomers having polyether chains; variousmonomers having a functional group such as an amide, cyano, hydroxyl,acidic group, neutralized acidic group, epoxy or hydrolyzable silylgroup; various monomers having poly(oxyethylene) chains; polyfunctionalvinyl monomers having two or more polymerizable double bonds permolecule; and the like.

Of these, representative examples of polymerizable monomers includevarious (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl(meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate,cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl(meth)acrylate, and the like; various ester crotonates such as methylcrotonate, ethyl crotonate, and n-butyl crotonate; the variousunsaturated diacidic dialkyl esters such as dimethylmaleate,dimethylfumarate, dibutylfumarate and dimethylitaconate; the variousmonocarboxyl vinyl esters such as vinylacetate, cyclohexane vinylcarboxylate, vinylbenzoate, and "VEOVA", (a branched chain mono carboxylvinyl ester produced by Shell Corporation, Holland); various aromaticvinyl monomers such as styrene, α-methyl styrene, p-tert-butyl styrene,and vinyl toluene; and the like.

From among vinyl monomers (a-2), representative examples of monomershaving one or more halogen atoms, such as fluorine or chlorine, permolecule include such (per)fluoroalkyl vinyl monomers as fluoroalkyl(meth)acrylates, perfluoroalkyl (meth)acrylates, perfluorocyclohexyl(meth)acrylate, di-perfluorocyclohexyl fumarate, and N-isopropylperfluorooctane sulfonamide ethyl (meth) acrylate; and variouschlorinated olefins such as vinyl chloride and vinylidene chloride.

From among vinyl monomer (a-2), representative examples of monomershaving a non-functional silicon atom include the various monomersrepresented by the general prepared: CH₂ ═CHCOO(CH₂)₃ [Si(CH₃)₂ O]_(n)Si(CH₃)₃, CH₂ ═C(CH₃)COOC₆ H₄ [Si(CH₃)₂ O]_(n) Si(CH₃)₃, CH₂═C(CH₃)COO(CH₂)₃ [Si(CH₃)₂ O]_(n) Si(CH₃)₃, CH₂ ═C(CH₃)COO(CH₂)₃[Si(CH₃) (C₆ H₅)O]_(n) Si(CH₃)₃, and CH₂ ═C(CH₃)COO(CH₂)₃ [Si(C₆ H₅)₂O]_(n) Si(CH₃)₃, (where n is 0, or an integer from 1˜130).

From among vinyl monomers (a-2), representative examples of monomershaving a polyether chain include monomers having a polyether segmentsuch as polyethylene glycol (meth)acrylate, polypropylene glycol(meth)acrylate, and the like. In particular, these may be used withinlimits which do not impair resistance to weathering and water.

From among vinyl monomers (a-2), representative examples of monomershaving an amide group include various vinyl monomers containing acarboxylic acid amide group such as N,N-dimethyl (meth)acrylamide,N-alkoxymethyl (meth)acrylamides, diacetone (meth)acrylamide, andN-methylol (meth)acrylamide.

From among the vinyl monomers (a-2), representative examples of themonomers having a cyano group include acrylonitrile, methacrylonitrile,crotononitrile and the like.

From among the vinyl monomers (a-2), representative examples of monomershaving a hydroxyl group include the various hydroxyalkyl (meth)acrylatessuch as 2-hyroxyethyl (meth)acrylate, 2-hyroxypropyl (meth)acrylate,2-hyroxybutyl (meth)acrylate, and 4-hyroxybutyl (meth)acrylate; andaddition products such as hydroxyalkyl (meth) acrylates andε-caprolactone.

From among the various vinyl monomers (a-2), representative examples ofmonomers having an acidic group include various unsaturated monobasicacids such as acrylic acid, (meth)acrylic acid and crotonic acid;various unsaturated dibasic acids such as maleic acid, fumaric acid,itaconic acid, and citraconic acid; half esters of the aforementionedunsaturated dibasic acids like maleic acid, fumaric acid and itaconicacid, and alkyl alcohols containing between 1 and 10 carbon atoms;aromatic compounds having carboxyl groups like 4-vinylbenzoic acid,cinnamic acid and the like; the products of addition reactions betweensaturated dibasic acids and monomers having hydroxy groups such assuccinic acid mono 2-(meth)acryloyloxyethyl ester and phthalic acid2-(meth)acryloyloxyethyl ester; mono vinyl esters having polycarboxylicacids such as malonic acid, succinic acid, adipic acid and sebacic acid;vinyl monomers having a phospholic acid group such as mono[2-(meth)acryololoxyethyl] acid phosphate; various vinyl monomerscontaining sulfonic acid group such as vinylsulfonic acid, allylsulfonicacid, 2-methyl allylsulfonic acid, 4-vinylbenzenesulfonic acid,2-(meth)acryloyl oxyethanesulfonic acid, 3-(meth)acryloyloxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, andthe like.

From among the vinyl monomers (a-2), representative examples of monomerswith a neutralized acidic group include various monomers having a saltform obtained by neutralizing a monomer having a carboxyl, sulfonic acidor phosphoric acid groups with a basic compound.

Representative examples of the basic compound employed when prepared amonomer having a neutralized acidic group include various inorganicbasic compounds like lithium hydroxide, sodium hydroxide, potassiumhydroxide, and ammonium hydroxide; as well as various organic basiccompounds like ethylamine, n-butylamine, dimethylamine, diethylamine,trimethylamine, triethylamine, tri-n-butylamine, diethanolamine,2-dimethylaminoethyl alcohol, tetramethylammonium hydroxide, andtetra-n-butylammonium hydroxide.

Representative examples of commercially available monomers having aneutralized acidic group include monomers having a neutralized sulfonicacid group such as "LATEMUL S-180" or "LATEMUL S-180A" (manufactured byKao Corp.) and "ELEMINOL JS-2" or "ELEMINOL RS-30" (manufactured bySanyo Chemical Industries, Ltd.); monomers having neutralized sulfuricacid group such as "AQUALON HS-10" (manufactured by Dai-ichi KogyoSeiyaku Co., Ltd.), and "ADEKA REASOAP SE-10N" (manufactured by AsahiDenka Kogyo K.K.); and monomers having a phosphoric acid group such as"NEW FRONTIER A-229E" (manufactured by Dai-ichi Kogyo Seiyaku Co.,Ltd.).

From among the vinyl monomers (a-2), representative examples of monomershaving an epoxy group include glycidyl(meth)acrylate,(β-methyl)glycidyl(meth)acrylate, 3,4-epoxycyclohexyl(meth)acrylate,allyl glycidyl ether, 3,4-epoxyvinylcyclohexane, di(β-methyl)glycidylmaleate, or di(β-methyl)glycidyl fumarate.

In the case of vinyl monomers (a-2) having a hydrolyzable silyl group,the term "hydrolyzable silyl" group as used indicates a silyl group suchas represented by the following general prepared, in which thefunctional group is readily hydrolyzable and produces a hydroxy groupbonded to a silicon atom upon hydrolysis. ##STR1##

(Wherein, R₁ indicates a monovalent hydrocarbon group selected from thegroup comprising alkyls, aryls, and aralkyls of 1 to 10 carbons; X₁indicates a monovalent group selected from the group comprising ahalogen atom, hydroxy group, alkoxy group, acyloxy, aminoxy, phenoxy,thioalkoxy, or amino group; and a indicates 0, 1 or 2.)

Representative examples of vinyl monomers having a hydrolyzable silylgroup include γ-(meth)acryloyloxypropyl trimethoxysilane,γ-(meth)acryloyloxypropyltriethoxysilane,γ-(meth)acryloyloxypropylmethyldimethoxysilane,γ-(meth)acryloyloxypropylmethyldiethoxysilane,γ-(meth)acryloyloxypropyltriisopropenyloxysilane, vinyltrimethoxysilane,vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy)silane,vinyltriacetoxysilane, vinyltrichlorosilane, andN-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, as well ashydrochlorides of these.

From among vinyl monomers (a-2), representative examples of monomershaving a functional group other than those cited above, include monomershaving a variety of functional groups, i.e., silyl esters of monomershaving a carboxyl group, such as trimethylsilyl(meth)acrylate andtert-butyldimethylsilyl (meth) acrylate; monomers having an acetal estergroup obtained by reacting an α,β-unsaturated ether compound and amonomer having a carboxyl group such as 1-ethoxyethyl (meth)acrylate or1-isobutoxyethyl (meth)acrylate; silyl ethers such as2-trimethylsiloxyethyl (meth)acrylate, and 2-dimethyl-tert-butylsiloxyethyl (meth)acrylate; monomers with an epoxy group such asglycidyl (meth)acrylate, allylglycidyl ethers, and the like; monomershaving aziridinyl group such as 2-aziridinylethyl (meth)acrylate;monomers having an isocyanate group like isocyanate ethyl(meth)acrylate, and (meth)acryloyl isocyanate; monomers having a blockedisocyanate group prepared by reacting a monomer having an isocyanategroup and a blocking agent; and monomers having a oxazoline group like2-isopropenyl-2-oxazoline or 2-vinyl-2-oxazoline.

From among the vinyl monomers (a-2), representative examples of monomershaving a poly(oxyethylene) chain include polyethylene glycolmono(meth)acrylate, polypropylene glycol mono(meth) acrylate,polytetramethylene glycol mono(meth)acrylate, monoalkoxypolyethyleneglycol (meth)acrylate, monoalkoxypolypropylene glycol (meth)acrylate,and the like.

From among vinyl monomers (a-2), representative examples ofmultifunctional vinyl monomers having two or more polymerizable doublebonds per molecule include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate,trimethylolpropane tri(meth)acrylate, polyethylene glycoldi(meth)acrylate, polypropylene glycol di(meth)acrylate,allyl(meth)acrylate, diallyl phtalate, divinylbenzene, and the like.

The amount of the employed vinyl monomer (a-1) containing a tertiaryamino group, which is one of the monomers cited above, is such that theamount of introduced tertiary amino group is between about 0.03 and 2.5moles per 1,000 grams of solid content of emulsion polymer (A)containing tertiary amino groups, with between 0.05 and 1.5 moles beingpreferable, and between 0.05 and 0.5 moles being even more suitable.

When the amount of the employed vinyl monomer (a-1) containing atertiary amino group is less than 0.03 moles, then the curing of thecoating tends to be insufficient. On the other hand, when the amountemployed exceeds 2.5 moles, then the coating tends to displayinsufficient resistance to chemicals, and the like.

It was found that when an acidic group is introduced into the emulsionpolymer (A) containing tertiary amino groups, by, for example, using amonomer containing an acidic group as one comonomer from among the othercopolymerizable vinyl monomers (a-2), it is possible to significantlyimprove the stability of polymerization when prepared emulsion polymer(A).

Moreover, it was found that by introducing the aforementioned acidicgroup, it is possible to even further improve curability in the presentinvention's curable resin composition for use in water-based coatingmaterials which includes emulsion polymer (A). Thus, a coating materialwhich is even more superior with respect to resistance to solvents andyellowing due to heat, and which provides a coating of even greaterhardness can be obtained. Carboxyl group is preferably employed as theacidic group which best coincides with this objective.

The amount of the aforementioned vinyl monomer containing an acidicgroup when the vinyl monomer containing an acidic group is copolymerizedwith at least a portion of vinyl monomer (a-2) is such that the amountof introduced carboxyl group is between about 0.05 and 3 moles per 1,000grams of solid content of emulsion polymer (A), with between 0.01 and2.0 moles being preferable, and between 0.01 and 0.7 moles being evenmore suitable.

It was found that when a hydroxyl group is introduced into emulsionpolymer (A), by, for example, using a monomer containing a hydroxylgroup as one comonomer from among the other copolymerizable vinylmonomers (a-2), it is possible to significantly improve the curabilityof the present invention's curable resin composition for use inwater-based coating materials, providing a coating which has even betterresistance to solvents, a higher degree of hardness and excellent filmappearance.

When copolymerizing the aforementioned monomers having a hydroxyl group,the copolymerization proportion is such that the amount of introducedhydroxyl group is around 0.04 to 2 moles, and preferably 0.08 to 1.2moles, per 1,000 grams of solid content of emulsion polymer (A).

Further, when a cycloalkyl group is introduced into emulsion polymer (A)as a copolymerizable vinyl monomer by employing various monomers havingcycloalkyl groups, such as cyclohexyl(meth)acrylate, for example, it ispossible to even further improve the resistance to weathering and waterof the present invention's curable resin composition for use inwater-based coating materials which includes emulsion polymer (A)Additionally, when a silane compound (C) such as those cited below isalso employed, the coating obtained offers an extremely high degree ofutility, having an even more superior film appearance and dirt sheddingresistance.

When introducing a cycloalkyl group into emulsion polymer (A), theamount employed of the monomer having the cycloalkyl group is such thatthe introduced cycloalkyl group is in the range of 0.5 to 5 moles, andpreferably 1.0 to 4.2 moles, per 1,000 grams of solid content ofemulsion polymer (A).

In the case of the above-cited emulsion polymer (A) containing tertiaryamino groups, which is an essential component of the present invention,the polymer may be one in which cross-links are formed in the emulsionparticles, or one in which cross-links are not formed. However, if crosslinks are formed in the emulsion particles, then the cured coat'sresistance to water, weathering and the like is even better.

Several methods may be employed to form cross links in the emulsionparticles of emulsion polymer (A). Namely, various monomers with ahydrolyzable silyl group, such as those cited above, may also beemployed as a component of the aforementioned vinyl monomer (a-2) ;monomers from among the aforementioned (a-2) components which react withtertiary amino groups in particular from among a monomer's functionalgroups may also be used; from among the above-cited components of vinylmonomer (a-2), and in particular, from among vinyl monomers havingfunctional groups, two or more different kinds of monomers which havemutually reactive functional groups may also be employed; or amultifunctional monomer may also be employed from among theaforementioned vinyl monomers (a-2).

As one example of a method for crosslinking within emulsion particles, amonomer having hydrolyzable silyl groups may be employed as one of thecomponents of vinyl monomer (a-2) to crosslink the emulsion particles inemulsion polymer (A), with the monomer having the hydrolyzable silylgroups employed in an quantity such that amount of hydrolyzable silylgroup introduced is in the range of 1 to 400 millimoles, and preferably2 to 20 millimoles, per 1,000 grams of solid content of emulsion polymer(A).

When preparing emulsion polymer (A) by carrying out emulsionpolymerization of a monomer mixture having the various above-citedtertiary amino vinyl monomers as the essential monomer component, in anaqueous medium, it is acceptable to employ one of the variousconventional emulsifying-polymerizing methods.

Namely, a polymerization reaction can be carried out according tovarious conventional methods using anionic emulsifying agent or nonionicemulsifying agent, various known non-reactive emulsifying agent orreactive emulsifying agent, or conventional dispersion stabilizers.

Representative examples of anionic emulsifying agent employed in thiscase include sulfuric esters of higher alcohols, alkyl benzenesulfonate, poly(oxyethylene)alkylphenyl sulfonate, and the like. Thesemay be used alone or in combinations of two or more.

Representative examples of non-ionic emulsifying agent includepoly(oxyethylene)alkyl ether, poly(oxyethylene)alkylphenyl ether,poly(oxyethylene)-poly(oxypropylene) block copolymer and the like.Naturally, these may be used alone or in combinations of two or more.

Representative examples of the above reactive emulsifying agent includea variety of monomers in salt forms, such as sulfonate, sulfate orphosphate, such as cited above as examples of the monomer (a-2) which iscopolymerizable with, but different from, the variety of monomers (a-1)having a tertiary amino group.

Representative examples of dispersion stabilizers include synthetic andnatural water-based macromolecules such as polyvinyl alcohol, celluloseether, starch, maleinized polybutadiene, maleinized alkyd resins,polyacrylic acid (salt), polyacryl amide, water-soluble acrylic resinsand the like. These maybe used alone, or in combinations of two or more.

From the perspective of obtaining a cured coating from the presentinvention's curable resin composition for use in water-based coatingmaterials which has particularly good resistance to water and the like,the amount of emulsifying agent used when prepared emulsion polymer (A)using carrying out emulsion polymerization method employing anemulsifying agent or dispersion stabilizer, is 10% by weight or less,and preferably 6% by weight or less, with respect to the solid contentin emulsion polymer (A).

Moreover, methods in which polymerization is carried out using verylittle or no emulsifying agent or the so-called "soap-free"polymerization method, are particularly preferred because of the evenfurther improvement realized in the water resistance of the curedcoating obtained from the composition according to the presentinvention.

Various soap-free polymerization methods are available, including 1) amethod in which polymerization is carried out primarily employing thereactive emulsifying agent mentioned above as an emulsifying agent; 2) amethod in which polymerization is carried out in the presence of a watersoluble acrylic resin from among the aforementioned various stabilizersin particular; 3) a method in which polymerization is carried out usingan aforementioned reactive emulsifying agent and a water soluble acrylicresin; as well as other methods. From among these, method 2 or method 3which employ a water soluble acrylic resin are particularly preferred.

The amount of emulsifying agent employed when carrying out soap-freepolymerization is less than 2% by weight, and preferably 1% by weight orless, with respect to the solid content in emulsion polymer (A).

The amount of dispersion stabilizer employed is within the range ofabout 5 to 70% by weight, and preferably 10 to 50% by weight, withrespect to the solid content of emulsion polymer (A). When the amount ofdispersion stabilizer employed is less than 5% or so, polymerizationstability deteriorates. Further, when the amount employed exceeds theaforementioned range, there is a marked increase in the viscosity of theresin, causing deterioration in the coating properties.

In the case of the water soluble acrylic resin used in carrying outemulsion polymerization of, a cationic water soluble acrylic resin maybe employed to partially or completely neutralize and make soluble inwater the acrylic resin with tertiary amino groups using an acidiccompound. Further, an anionic water soluble acrylic resin may beemployed for partially or completely neutralizing and making soluble inwater an acrylic resin with carboxyl groups using a basic compound.

From among these, from the perspective of resistance to water andadhesive character, an anionic water soluble acrylic resin is preferablyemployed.

The anionic water soluble acrylic resin employed here is preferably aresin which has functional groups which reacts with reactive functionalgroups in tertiary amino vinyl monomer (a-1), or with the functionalgroups in the other copolymerizable vinyl monomer (a-2), and/or is aresin having radical polymerizable unsaturated double bonds for whichgraft polymerization is possible when preparing emulsion polymer (A).

The water-based medium employed when preparing this emulsion polymer (A)is not particularly limited. Rather, water alone, or a mixture of waterand a water soluble organic solvent may be used.

Representative examples of the water soluble organic solvent (watersoluble solvent) employed here include various alcohols such as methylalcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethylcellosolve, and butyl cellosolve; and various polar solvents such asN-methyl pyrolidone. These may be used alone or in combinations of twoor more.

In the case where a mixture of water and a water soluble solvent isemployed, it is preferable to optimally select the amount of watersoluble solvent employed in view of stability during polymerization.However, in view of the flammability and sanitation of the obtainedwater-based dispersed solution of the polymer, it is desirable that theamount of the water soluble solvent be extremely small. Accordingly,from this perspective, it is preferable to use waLer itself as thesolvent.

Various polymerization methods are available when prepared emulsionpolymer (A), including: a method in which water, an emulsifying agentand/or dispersion stabilizer, a polymer catalyst, and a monomercomponent (a) having as essential components a tertiary amino vinylmonomer (a-1) and another copolymerizable vinyl monomer (a-2), are mixedtogether all at once; a monomer drop method in which a monomer component(a) is added by dropping; and a pre-emulsion method in which water, amonomer component (a) and an emulsifying agent are premixed and thenadded by dropping. Any of these various methods may be employed toprepare the emulsion polymer (A) containing tertiary amino groups whichis employed in the present invention.

However, preparation using the monomer drop method or the pre-emulsionmethod is preferable from the perspective of stability at the time ofpolymerization.

It is also possible to add a hydrophilic or hydrophobic solvent, orvarious conventional additives, when carrying out the polymerizationreaction. However, the amount of these additives must be within limitswhich do not adversely affect the various properties of the curedcoating obtained from the present invention's curable resin compositionfor use in water-based coating materials.

When preparing emulsion polymer (A), a radical polymerization initiatormay be employed as a polymerization initiator. Representative examplesof radical polymerization initiators include various inorganic peroxidessuch as potassium persulfate, ammonium persulfate, and hydrogenperoxide; various organic peroxides such as tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, and cumene hydroperoxide; and various azoinitiators such as 4,4'-azobis (4-cyanovaleric acid),2,2'-azobis(2-amidinopropane)dihydrochloride, and the like.

In the case where using a peroxide as the polymerization initiator, theradical polymerization reaction may be carried out using the peroxidealone, or using a so-called redux polymerization initiator which employsboth a peroxide and a reducing agent such as an acidic sodium sulfite orsodium thiosulfate.

Further, various chain transfer agents may be employed as a molecularweight adjust agent, such as lauryl mercaptan, octyl mercaptan, dodecylmercaptan, 2-mercaptoethanol, octyl thio glycolate, 3-mercaptopropionicacid, α-methyl styrene dimer, and the like.

The polymerization temperature when preparing emulsion polymer (A) willvary depending on the type of monomer used, polymerization initiatorused, etc. Furthermore, in the case where carrying out polymerization ina water-based medium, a temperature in the range of 30° C. to 90° C. ispreferable.

The tertiary amino groups contained in emulsion polymer (A) may beneutralized with an acid, or may not be neutralized. However, sincethere is a possibility that stability may deteriorate and a block occurwhen preparing emulsion polymer (A) or when the storage stability or thestability at the time of use is not sufficient, then the stability maybe improved by using acid to neutralize at least a portion of thetertiary amino groups.

To prepared an emulsion polymer (A) in which at least a portion of itstertiary amino groups have been neutralized, various methods may besuitably employed, such as carrying out polymerization using a vinylmonomer (a-1) having a tertiary amino group which has beenpre-neutralized using an acidic compound; neutralizing the tertiaryamino groups by adding an acidic compound during polymerization; orneutralizing by adding an acidic compound after preparing emulsionpolymer (A).

Particularly representative examples of acidic compounds which can beused in this instance include carboxylic acids with between 1 and 10carbon atoms such as formic acid, acetic acid, propionic acid, butyricacid, 2-methyl butyric acid, iso-valeric acid, trimethyl acetic acid,glycolic acid and lactic acid; mono- or dialkyl esters of phosphoricacid such as phosphoric acid monomethyl ester, phosphoric acid dimethylester, phosphoric acid mono-iso-propyl ester, phosphoric aciddi-iso-propyl ester, phosphoric acid mono-2-ethylhexyl ester, andphosphoric acid di-2-ethylhexyl ester; organic sulfonic acids such asmethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid,dodecyl benzenesulfonic acid; and various inorganic acids such ashydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. Amongthe above acidic compounds however, the carboxylic acids areparticularly preferred.

When improving stability by adding these acidic compounds, the amount ofacidic compounds employed is preferably such that the ratio of theequivalent weight of the acidic compound with respect to that of thetertiary amino groups included in emulsion polymer (A), i.e., acidiccompound/tertiary amino groups equivalent weight ratio, is about 0.1 ormore. Furthermore, in order not to impair the properties of the coatingfilm prepared, a ratio of between 0.1 and 3 is preferred, with a ratioof between 0.1 and 2 being even more suitable.

When preparing emulsion polymer (A) containing tertiary amino groups, inthe case where acidic groups are introduced into emulsion polymer (A) byusing a vinyl monomer having an acidic group as the othercopolymerizable vinyl monomer (a-2), the acidic group may be neutralizedusing a basic compound, or may not be neutralized. However, it ispreferable to neutralize at least a portion of the acidic groups with abasic compound, with a view toward decreasing block generation byimproving stability during preparation of emulsion polymer (A), and witha view toward improving stability during storage and use.

Various methods may be suitably employed when prepared emulsion polymer(A) having neutralized acidic groups, including a method in which vinylmonomers having acidic group which have been pre-neutralized with abasic compound are copolymerized; a method in which the acidic groupsare neutralized by adding basic compound during polymerization; and amethod in which neutralization is carried out by adding the basiccompound after preparing emulsion polymer (A).

Conventional compounds maybe employed for the aforementioned basicsubstance, including various alkali metal compounds such as sodiumhydroxide and potassium hydroxide; various alkali earth metal compoundssuch as calcium hydroxide and calcium carbonate; ammonia; and variouswater soluble organic amines such as monomethyl amine, dimethyl amine,trimethyl amine, monoethyl amine, diethyl amine, triethyl amine,monopropyl amine, dimethyl propyl amine, monoethanol amine, diethanolamine, triethanol amine, ethylene diamine, and diethylene triamine.These may be used alone or together.

When further improvement in water resistance of the coating of emulsionpolymer (A) is desired, for example, it is preferable to employ alow-boiling point amine such as ammonia or triethyl amine, whichvolatilizes at room temperature or upon heating.

When neutralizing the acidic groups included in polymer (A) using thesebasic compounds, the amount added is such that the ratio of theequivalent weight of the basic groups in the basic compound to that ofthe acidic groups included in emulsion polymer (A) containing tertiaryamino groups, i.e., weight equivalent ratio of basic compound/acidicgroups in emulsion polymer (A) containing tertiary amino groups, is 0.1or greater. Moreover, a weight equivalent ratio in the range of 0.1 to 3is preferred as a range which will not impair the properties of theobtained coating, with a range of 0.1 to 2 being even more suitable.

The number-average molecular weight of a thus-prepared emulsion polymer(A) is roughly 5,000 or greater, with 30,000 or greater being preferred,and 50,000 or greater being even more suitable.

The concentration of the solid content in emulsion polymer (A)containing tertiary amino groups is preferably around 20 to 70 byweight, and more preferably 20 to 60% by weight.

By setting the concentration of the solid content to be 70% by weight orless, it is possible to restrict an abnormal increase in viscosity ofthe polymer, facilitating heat removal during polymerization of themonomer. Accordingly, emulsion polymer (A) can be easily and stablyprepared.

Further, setting the concentration of the solid content to be 60% byweight or less is even more desirable, since, in this case, theviscosity of polymer (A) is within the range demanded for variousapplications.

On the other hand, in view of productivity and the like, it ispreferable to set the concentration of the solid content to be about 20%by weight or more.

The particle diameter of emulsion polymer (A) is not particularlyrestricted. For example, an average particle diameter in the range of 30to 1,000 nm is preferable from the perspective of ease of filmformation.

Next, representative examples of vinyl polymers having both epoxy groupsand hydrolyzable silyl groups, silane coupling agents having epoxygroups, and silicone resins having both epoxy groups and hydrolyzablesilyl groups will be cited as examples of compound (B) which has both,at least, an epoxy group and a hydrolyzable silyl group in a singlemolecule.

Hydrolyzable silyl group as used here refers to groups of atoms whichcontain a silicon atom which is bonded to, for example, a halogen atom,or an alkoxy, substituted alkoxy, phenoxy, isopropenyloxy, acyloxy oriminooxy group, and which are easily hydrolyzable to form a silanolgroup. Particularly representative examples include the alkoxy silyl,phenoxy silyl, halo silyl, isopropenyloxy silyl, acyloxy silyl, andiminooxy silyl groups.

Any of wellknown methods can be used to prepare the vinyl polymerscontaining these two reactive groups as specified above, but therecommended methods include: (i) a solution radical copolymerization ofa vinyl monomer containing epoxy groups and a vinyl monomer containing ahydrolyzable silyl group, such as those compounds cited above ascopolymerizable monomers employed when preparing emulsion polymer (A);(ii) a solution radical copolymerization of a mixture of monomers whichinclude one of the various epoxy vinyl monomers mentioned above, one ofvarious vinyl monomers with hydrolyzable silyl groups, and another vinylmonomer which is co-polymerizable with these; (iii) a solution radical(co)polymerization of a mixture of monomers which include one of theaforementioned various epoxy vinyl monomers as an essential monomercomponent, in the presence of one of the various chain transfer agentswhich include a hydrolyzable silyl group, such as γ-mercaptopropyltrimethoxy silane, γ-mercaptopropyl triethoxy silane, γ-mercaptopropylmethyldimethoxy silane, γ-mercaptopropyl triisopropenyloxy silane, orthe like; and (iv) other methods which suitably combine the precedingmethods (i) or (ii) with method (iii).

Representative examples of the epoxy silane coupling agents mentionedabove include various epoxy silane compounds such asγ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxy silane,β-(3,4-epoxycyclohexyl)ethyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, andγ-glycidoxypropyltriisopropenyloxysilane; the addition products ofvarious isocyanato silane compounds, such as γ-isocyanato propyltriisopropenyloxy silane or γ-isocyanato propyl trimethoxy silane, withglycidol; the addition products of various amino silane compounds, suchas γ-aminopropyl trimethoxy silane, with diepoxy compounds; or compoundswhich contain two or more hydrolyzable silyl groups and two or moreepoxy groups in a molecule, formed by a partial hydrolysis condensationof the various epoxy silane compounds mentioned above.

Particularly representative examples of the aforementioned siliconeresins which contain both epoxy and hydrolyzable silyl groups are thecyclic tetra siloxanes, the general formula of scheme (2) for which isshown below. ##STR2## (Note, the Gly in this diagram represents a3-glycidoxy propyl group.)

In the preparation of a curable resin composition for use in water-basedcoating materials detailed in this invention, which contains theaforementioned emulsion polymer (A) containing tertiary amino groups andcompound (B) containing both an epoxy and a hydrolyzable silyl groups asessential film-forming components, the two constituents (A) and (B)should be mixed together in a proportion that will yield a molar ratioof the tertiary amino group in emulsion polymer (A) to the epoxy groupin compound (B) in the range of about 0.1 to 5, and preferably 0.3 to3.0, and even more preferably, in the range of 0.5 to 2.0. (However, inthe case where emulsion polymer (A) contains acidic groups, the molarnumber of the acidic groups is also added to the molar number of thetertiary amino groups in the emulsion polymer (A)).

Next, an explanation will be made of the method of preparation ofwater-based compound (C), an additional essential component of thepresent invention, which is obtained by adding a neutralizing agent to avinyl polymer (I) containing carboxyl groups and/or tertiary aminogroups so that at least 10% of the acidic groups and/or tertiary aminogroups are neutralized, and then dispersing or dissolving in water.

To begin with, representative examples of vinyl polymers (I) containingcarboxyl groups and/or tertiary amino groups include the variousacrylic, aromatic vinyl, vinyl ester, and fluoro olefin polymers.

From among these vinyl polymers (I), acrylic polymers and fluoro olefinpolymers are particularly preferred.

Vinyl polymers (I) include 1) vinyl polymer (I-1) containing tertiaryamino groups, 2) vinyl polymer (I-2) containing both carboxyl groups andtertiary amino groups, and 3) vinyl polymer (I-3) containing carboxylgroups. Respectively, these include:

(α) water-based compound (C-1) obtained using vinyl polymer (I-1) and anacidic compound as a neutralizing agent,

(β) water-based compound (C-2) obtained using vinyl polymer (I-2) and anacidic compound as a neutralizing agent,

(γ) water-based compound (C-3) obtained using vinyl polymer (I-2) and abasic compound as a neutralizing agent, and

(δ) water-based compound (C-4) obtained using vinyl polymer (I-3) and abasic compound as a neutralizing agent.

Water-based compound (C-1), which is obtained by using an acidiccompound to partially or completely neutralize vinyl polymer (I-1) whichhas tertiary amino groups, and then dispersing or dissolving in water,will be explained below.

Vinyl polymer (I-1) containing tertiary amino groups can be easilyprepared using a variety of wellknown methods. For example, a methodsuch as (1) copolymerizing a vinyl monomer containing a tertiary aminogroup with another copolymerizable monomer, or (2) carrying out adehydrative imidization treatment following the addition reaction of acompound containing both tertiary amino and primary amino groups to avinyl polymer containing acid anhydride groups, as disclosed in JapanesePatent, First Publication No. Sho 59-56243, may be suitably employed.

Of these, method (1) above is the most simple and convenient to carryout, and is thus most suitable.

Particularly suitable examples of the tertiary amino vinyl monomers usedto prepare the tertiary amino vinyl polymer (I-1) described inpreparation method (1) above include the various compounds cited abovewhich are employed in the preparation of emulsion polymer (A). Further,suitable examples of the other vinyl monomers which are copolymerizablewith the various aforementioned tertiary amino vinyl monomers includethose compounds cited above which are employed in the preparation ofpolymer (A).

When preparing a fluoro olefin polymer from among these various vinylpolymers, fluoro olefin and a tertiary amino monomer may be employed asthe essential starting components, with monomers copolymerizable withthese also used as necessary.

Representative examples of the fluoro olefin employed in this caseinclude vinyl fluoride, vinylidene fluoride, trifluoroethylene,tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene.

When preparing a tertiary amino vinyl polymer (I-1) from these variousmonomers, one of the wellknown methods may be employed. However, fromamong these, a solution radical polymerization method is recommended asit is the easiest employed.

Representative examples of solvents used in this case include varioushydrocarbons like toluene, xylene, cyclohexane, n-hexane and octane; thevarious alcohol solvents such as methanol, ethanol, iso-propanol,n-butanol, iso-butanol, sec-butanol, ethylene glycol monomethyl ether,ethylene glycol mono ethyl ether, ethylene glycol mono iso-propyl ether,and ethylene glycol monobutyl ether; the various esters such as methylacetate, ethyl acetate, n-butyl acetate, and amyl acetate; and thevarious ketone solvents such as acetone, methyl ethyl ketone, methyliso-butyl ketone, and cyclohexanone. All of these solvents may be usedseparately or in mixtures of 2 or more solvents. Water may also beadded.

Polymerization can be carried out by normal methods, using the selectedsolvent and any well-known radical polymerization initiators such as azoor peroxide compounds. Furthermore, if required, chain transfer reagentssuch as those cited above which are application when preparing emulsionpolymer (A) may be used as molecular weight adjusting agents.

A tertiary amino vinyl polymer (I-1) prepared in this way should containbetween about 0.03 and 2.5 moles of tertiary amino groups per 1,000grams of solid content of polymer (I-1), with between 0.05 and 1.5 molesbeing preferable, and between 0.05 and 0.5 moles being even moresuitable.

Furthermore, the number-average molecular weight for the polymer (I-1)should be in the range of about 500 to 100,000, and preferably in therange 1,000 to 30,000.

Moreover, in cases where hydroxyl groups are introduced into the vinylpolymer (I-1) containing tertiary amino groups, by for example using amonomer containing a hydroxyl group as one of the comonomer cited above,then the curability of this invention's composition, which will containthe water-based product (C-1) formed from this polymer (1-1) as theessential component for the formation of the coating film, can beimproved even further, producing a coating film which has even betterfilm appearance, even better resistance to solvents, and an even greaterlevel of hardness.

In those instances where hydroxyl group is introduced into the vinylpolymer (I-1) containing tertiary amino groups, then 1,000 grams ofsolid content of polymer (I-1) should contain between 0.04 and 2 moles,and preferably between 0.08 and 1.2 moles, of hydroxyl group.

By adding an acidic compound to the tertiary amino vinyl polymer (I-1)prepared by the method mentioned above, the tertiary amino groups in thepolymer are partially or completely neutralized, and a polymer which issoluble or dispersible in water is prepared.

Particularly representative acidic compounds which can be used in thisinstance include those acidic compounds cited above, with carboxylicacids being particularly preferred from among these.

The quantity of acidic compound to be added to the polymer (I) should beat least enough to generate dispersibility in the vinyl polymer (I-1)outlined above, and the ratio of the equivalent weight of the acidiccompound to that of the tertiary amino groups included in vinyl polymer(I-1), in other words: acidic groups in the acidic compound/tertiaryamino groups in polymer (I-1) weight equivalent ratio, should be 0.1 orgreater, but in order not to impair the properties of the coating filmgenerated, a ratio of between 0.1 and 3 is preferred, with a ratio ofbetween 0.1 and 2 being even more suitable.

The previously mentioned water-based product (C-1) can be prepared fromthe thus prepared neutralized vinyl polymer (I-1) using variouswellknown methods. For example, water can be simply added to theneutralized material, or alternatively, the neutralized material addedto water to produce the water-based product (C-1).

Furthermore, the water-based product (C-1) can be prepared, as required,with either partial, or complete removal of the organic solvent used inthe preparation of the tertiary amino vinyl polymer (I-1), by removingthe solvent under heat, or under reduced pressure. Accordingly, awater-based product (C-1) can be prepared which contains very little orno organic solvent.

Next, we will explain the previously mentioned water-based product(C-2), obtained by dispersing or dissolving in water, a vinyl polymer(I-2) containing both tertiary amino groups and carboxyl groups to whichhas been added an acidic compound so that the ratio of the equivalentweight of acidic groups in the added acidic compound to that of thetertiary amino groups in the vinyl polymer (I-2) is at least 0.1.

This vinyl polymer (I-2) containing both tertiary amino groups andcarboxyl groups can be prepared by various wellknown methods. Forexample, (3) a mixture of monomers containing a tertiary amino vinylmonomer and an acidic vinyl monomer can be polymerized; (4) as presentedin Japanese Patent, First Publication, No. Sho 59-56243, a vinyl polymercontaining a carboxylic acid anhydride group can be reacted with acompound whici contains a tertiary amino group and a group with anactive hydrogen; (5) a vinyl polymer containing hydroxyl and tertiaryamino groups can be reacted with a dicarboxylic acid anhydride; or (6) amixture of monomers containing a vinyl monomer containing a tertiaryamino group, and a vinyl monomer containing a blocked acidic group suchas a trialkyl silyl ester group, a hemiacetal ester group, or atert-butyl ester group, which can easily be converted to a free acidicgroup by the action of acid, heat or water, can be polymerized,producing a vinyl polymer with tertiary amino and blocked acidic groups,which can then have the blocked acidic groups converted to free acidicgroups. Among the methods outlined, method (3) is particularlyrecommended, because it is the most simple and convenient.

The vinyl monomer containing a tertiary amino group required to preparethe vinyl polymer (I-2) containing both tertiary amino and acidic groupsby method (3) above, can be any of the various vinyl monomers containinga tertiary amino group mentioned previously which may be employed in thepreparation of emulsion polymer (A).

Furthermore, particularly suitable vinyl monomers containing acidicgroup for the preparation of this vinyl polymer (I-2) include thevarious vinyl monomers containing carboxyl acid groups, phosphoric acidgroups or sulfonic acid groups, which are applicable in the preparationof emulsion polymer (A). Among these, the use of monomers containingcarboxylic acid group is desirable.

Furthermore, other copolymerizable vinyl monomers which can be used inthe preparation of the vinyl polymer (1-2) include the various vinylmonomers previously mentioned in the discussion regarding preparation ofemulsion polymer (A).

In the case where preparing a fluoro olefin polymer from among the vinylpolymers (I-2), fluoro olefins cited above in connection with thepreparation of tertiary amino vinyl polymer (I-1) may be employed as theessential monomer component.

In an example of preparation of the vinyl polymer (I-2) from the variousaforementioned monomers, both solvents and initiators can be usedaccording to the preparation method of the vinyl polymer (I-1).

A vinyl polymer (I-2) prepared in this method should contain betweenabout 0.03 and 2.5 moles of introduced tertiary amino groups per 1,000grams of solid content of polymer (I-2), with between 0.05 and 1.5 molesbeing preferable, and between 0.05 and 0.5 moles being even moresuitable.

Furthermore, a vinyl polymer (I-2) prepared in this method shouldcontain acidic groups in the amount of about 0.07 to 5.0 moles, withbetween 0.07 and 2.0 moles being preferable, and between 0.1 and 0.7moles being even more suitable. Moreover, the number-average molecularweight for vinyl polymer (I-2) should be in the range of about 500 to100,000, and preferably in the range of 1,000 to 30,000.

Furthermore, in cases where hydroxyl groups are introduced into thevinyl polymer (I-2) containing both tertiary amino and acidic groups, byfor example using a monomer containing a hydroxyl group as one of thecomonomers cited above, then the curability of this invention'scomposition, which will contain the water-based product (C-2) formedfrom this polymer (I-2) as the essential component for the formation ofthe coating film, can be improved further, producing a coating filmwhich has an even better film appearance and resistance to solvents, aswell as a higher level of hardness.

In those instances where hydroxyl groups are introduced into the vinylpolymer (I-2) containing both tertiary amino and acidic groups, then1,000 grams of solid content of polymer (I-2) should contain between0.04 and 2 moles, and preferably between 0.08 and 1.2 moles, of hydroxylgroups.

By adding an acidic compound to the vinyl polymer (I-2) containing bothtertiary amino and acidic groups formed by the method mentioned above,the tertiary amino groups in the polymer are partially, or completelyneutralized, and a polymer which is soluble or dispersible in water isprepared.

The acidic compound used in this step can be any of the acidic compoundsmentioned previously as being suitable in the preparation of thewater-based product (C-1), but of these, carboxylic acids are the mostsuitable.

The quantity of the acidic compound to be added to the polymer should besufficient to ensure that the ratio of the equivalent weight of acidicgroups in the added acidic compound to that of the tertiary amino groupsin the vinyl polymer (I-2) is at least 0.1, with a ratio of between 0.1and 3 preferred, and a ratio of between 0.1 and 2 being even moresuitable.

The previously mentioned water-based product (C-2) can be prepared fromthe thus prepared neutralized vinyl polymer (I-2) prepared by thismethod, containing both tertiary amino and acidic groups, by the samemethods outlined above for preparing the water-based product (C-1) fromthe neutralized vinyl polymer (I-1).

Next, we will explain the previously mentioned water-based product(C-3), obtained by adding a basic compound to a vinyl polymer (I-2)containing both tertiary amino and acidic groups so that the weightequivalent ratio of basic groups in the added basic compound to acidicgroups in the vinyl polymer (I-2) is at least 0.1, and then dispersingor dissolving in water.

Firstly, the vinyl polymer (1-2) containing both tertiary amino andacidic groups can be prepared by the method already described in thediscussion concerning the preparation of water-based product (C-2).

Furthermore, in cases where hydroxyl groups are introduced into thevinyl polymer (I-2) containing both tertiary amino and acidic groups,by, for example, using a monomer containing a hydroxyl group as onecomonomer, then the curing properties of this invention's composition,which will contain the water-based product (C-3) prepared from thispolymer (I-2), can be improved even further, preparing a coating filmwhich has even better film appearance, even better resistance tosolvents, and an even greater level of hardness.

In those instances where hydroxyl groups are introduced into the vinylpolymer (I-2) containing both tertiary amino and acidic groups, then1,000 grams of solid content of polymer (I-2) should contain between0.04 and 2 moles, and preferably between 0.08 and 1.2 moles, of hydroxylgroups.

By adding a basic compound as a neutralizer to the vinyl polymer (I-2)containing both tertiary amino and acidic groups prepared by the methodmentioned above, the acidic groups in the polymer are partially orcompletely neutralized, and a polymer which is soluble or dispersible inwater is prepared.

Particularly representative examples of basic compounds which can beused in this instance include the various compounds cited above inconnection with the preparation of emulsion polymer (A), wherein, fromamong the various basic compounds cited, ammonia and various organicamines are particularly preferred.

The quantity of basic compound to be added to the polymer should besufficient to ensure that the ratio of the equivalent weight of thebasic groups in the added basic compound to acidic groups in the vinylpolymer (I-2) is at least 0.1, with a ratio of between 0.1 and 3 beingpreferred, and a ratio of between 0.1 and 2 being more suitable.

In order to prepare the water-based product (C-3) from the thus formedmixture of basic compound and vinyl polymer (I-2) having tertiary aminoand acidic groups, the same methods outlined above for preparing thewater-based product (C-1) from the neutralized vinyl polymer (I) can beused.

Next, we will explain the previously mentioned water-based product(C-4), obtained by dispersing or dissolving an acidic vinyl polymer(I-3) in water which has been partially or completely neutralized by abasic compound.

This acidic vinyl polymer (I-3) can be prepared by various wellknownmethods. For example, (7) a vinyl monomer containing an acidic group canbe copolymerized with another copolymerizable vinyl monomer; (8) a vinylmonomer containing a hydroxyl group can be reacted with a dicarboxylicacid anhydride; or (9) as was described previously, a vinyl monomer witha blocked acidic group can be copolymerized with another suitable vinylpolymer, and the blocked acidic group then converted to a free acidicgroup.

Of these methods, method (7) is recommended as it is the simplest andmost convenient.

The vinyl monomer containing an acidic group required to prepare thevinyl polymer (I-3) containing an acidic group by method (7) above can,of course, be any of the various acidic vinyl monomers mentionedpreviously as suitable monomers for the production of the vinyl polymer(I-2) containing both tertiary amino and acidic groups.

Of these, monomers containing carboxylic acid group are particularlysuitable.

Furthermore, other copolymerizable vinyl monomers which can be used inthe preparation of the vinyl polymer (I-3) include, of course, thevarious vinyl monomers previously mentioned in the discussion regardingpreparation of vinyl polymer (I-1).

In the case where preparing fluoro olefin polymer from among theaforementioned vinyl polymers (I-3), fluoro olefins cited in connectionwith the preparation of vinyl polymer (I-1) containing tertiary aminogroups may be employed as the essential monomer component.

Similar solvents and initiators used in the preparation of the vinylpolymer (I-3) may also be selected, respectively from those mentionedearlier in this invention for production of vinyl polymer (I-1).

A vinyl polymer (I-3) prepared in this method should contain betweenabout 0.07 and 5.0 moles of introduced acidic groups per 1,000 grams ofsolid content of polymer (I-3), with between 0.3 and 2.0 moles beingpreferable. Furthermore, the number-average molecular weight for thevinyl polymer (I-3) should be in the range of about 500 to 100,000, andpreferably in the range of 1,000 to 30,000.

Moreover, in cases where hydroxyl groups are introduced into the vinylpolymer (I-3) containing acidic groups, by, for example, using a monomercontaining a hydroxyl group as a comonomer, then the curability of thisinvention's composition, which will contain the water-based product(C-4) formed from this polymer (I-3) as the constituent necessary forthe preparation of the coating film, can be improved even further,preparing a coating film which has even better film appearance, evenbetter resistance to solvents, and an even greater level of hardness.

In those instances where hydroxyl groups are introduced into the vinylpolymer (I-3) containing acidic groups, then 1,000 grams of solidcontent of polymer (I-3) should contain between 0.04 and 2 moles, andpreferably between 0.08 and 1.2 moles of hydroxyl groups.

By adding a basic compound to the vinyl polymer (I-3) containing anacidic group prepared by the method mentioned above, the acidic groupsin the polymer (I-3) are partially or completely neutralized, and then apolymer which is soluble or dispersible in water is prepared.

The basic compound used in this method can, of course, be any of thecompounds mentioned previously as being suitable in the preparation ofthe water-based product (C-4), but among them, ammonia and organicamines are suitable.

The quantity of basic compound to be added to the polymer, should besufficient to ensure that the ratio of the equivalent weight of thebasic groups in the added basic compound to that of the acidic groups inthe vinyl polymer (I-3) is at least 0.1, with a ratio of between 0.1 and3 being preferred, and a ratio of between 0.1 and 2 being even moresuitable.

In order to prepare the water-based product (C-4) from the thus formedmixture of vinyl polymer (I-3) containing acidic groups and basiccompound, the same method as outlined above for preparing thewater-based product (C-1) from the neutralized vinyl polymer (I-1) maybe used.

When preparing the present invention's curable resin composition for usein water-based coating materials from emulsion polymer (A), compound (B)containing, at least, an epoxy group and a hydrolyzable silyl group, andwater-based compound (C), component (B) is mixed into a base resinobtained by mixing component (A) and component (C) so that the weightratio of the solid content of (A) to the solid content of (C) is in therange of about 98/2 to 2/98, with a range of 95/5 to 5/95 beingpreferred and 85/15 to 15/85 being even more suitable, so that the ratioof the total molar number of tertiary amino and acidic groups includedin component (A) and component (C) to the molar number of epoxy groupsincluded in component (B) is in the range of about 0.1 to 5.0, with arange of 0.3 to 3 being preferred and 0.5 to 2.0 being even moresuitable.

Furthermore, by removing compound (B) containing an epoxy and ahydrolyzable silyl groups from a composition comprising components (A),(B) and (C), and adding a compound (D) containing hydrolyzable silyland/or silanol groups, it is possible to even further improve the curedcoating's resistance to weathering, corrosion, water and dirt shedding,while also increasing the hardness thereof.

Representative examples of compound (D) containing hydrolyzable silyland/or silanol groups include silicate compounds like methyl silicate,ethyl silicate, isopropyl silicate, and n-butyl silicate; silicateoligomers obtained by partial hydrolysis and condensation of theaforementioned silicate compounds; various trifunctional silanecompounds such as methyltrimethoxysilane, phenyl trimethoxysilane,methyltriethoxysilane, phenyltriethoxysilane, andisobutyltrimethoxysilane; various difunctional silane compounds such asdimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane,diethyldiethoxysilane, and diphenyldimethoxysilane; low molecular weightsilanol compounds obtained by virtually complete hydrolysis of thetrifunctional and difunctional silane compounds mentioned above, or ofthe various halo silanes such as methyltrichlorosilane,phenyltrichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, anddiphenyldichlorosilane; linear or cyclic polysiloxanes containingsilanol group, obtained by carrying out a dehydration condensation onthe silanol compounds mentioned above; and linear, branched or cyclicpolysiloxanes containing alkoxysilyl group, obtained by carrying out apartial hydrolysis and condensation on at least one of the compoundsfrom the group of aforementioned difunctional and trifunctional silanecompounds and silicate compounds.

When preparing the present invention's curable resin composition for usein water-based coating materials comprising components (A), (B), (C),and, additionally, (D), the amount of aforementioned compound (D) addedto a composition obtained by mixing the three components (A), (B), and(C) at the proportions cited above should be within a range of about 0.5to 200 parts by weight, and preferably 1 to 100 parts by weight, withrespect to 100 parts by weight of the solid content of the resins fromcomponents (A) and (C).

Furthermore, if necessary, a curing catalyst (E) may be added to thecurable resin compositions for use in water-based coating materialsdescribed in this invention. Addition of such a catalyst results in animprovement in the curability of the compositions.

Representative examples of the catalyst (E) include various basiccompounds such as lithium hydroxide, sodium hydroxide, potassiumhydroxide, and sodium methylate; various metallic compounds such astetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, leadoctylate, cobalt octylate, zinc octylate, calcium octylate, zincnaphthenate, cobalt naphthenate, di-n-butyl tin diacetate, di-n-butyltin dioctoate, di-n-butyl tin dilaurate and di-n-butyl tin maleate; andvarious acidic compounds such as p-toluenesulfonic acid, trichloroaceticacid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoricacid, monoalkyl phosphonic acid and dialkyl phosphonic acid.

Furthermore, if necessary, various wellknown additives may be added tothe curable resin compositions for use in water-based coating materialsdescribed in this invention. Such additives include various coalescingagents such as isopropyl alcohol, sec-butanol, n-butanol, 2-ethylhexanol, 2-propoxy ethanol, 2-n-butoxy ethanol, 2-n-propoxy propanol,3-n-propoxy propanol, 2-n-butoxy propanol, 3-n-butoxy propanol,2-n-butoxyethyl acetate, diethylene glycol monobutyl ether,N-methylpyrrolidone, 2,2,4- trimethyl-1,3-pentanediol monobutarate,dibutyl phthalate ester and butylbenzyl phthalate ester; fillers;organic pigments; inorganic pigments; metallic pigments such asaluminum; pH adjusters; leveling reagents; thickeners; water repellents;anti-foaming agents; plasticizers; antioxidants; UV absorbers;anticratering agent; anti-skinning agent; dispersing agents; and thelike.

When using the curable resin compositions for use in water-based coatingmaterials described in this invention, and outlined above, a so-calledtwo component system is used with the constituent compound (B)containing both epoxy and hydrolyzable silyl groups being mixed with theother constituents immediately before use. The mixture should then bepainted within one day (24 hours), with paint inside of 12 hours beingpreferable. Particular care needs to be taken in this respect, as ifleft for more than one day, the curability at room temperature of thecomposition decreases markedly.

The curable compositions for use in water-based coating materialsdescribed in this invention can be used with conventional methods topaint various substrates, and then either dried at room temperature forbetween 1 and 10 days, force dried at between 40 and 100° C. for between1 and 60 minutes, or bake dried at between 100 and 180° C. for between 1and 60 minutes. This process provides an excellent coating film that hasexcellent weather resistant, and excellent resistance to solvents,chemicals and water.

EXAMPLES

Next, we will attempt to explain the invention in more concrete terms,by giving reference, working and comparative examples. Note, however,that this in no way implies that the invention is limited to theexamples illustrated. Unless specified otherwise, reference in theseexamples to `parts` or `percentages` refers to weight standards.

Reference Example 1

[Preparation of an emulsion polymer (A) containing tertiary aminogroups]

Deionized water in the amount of 1,500 parts was added to a reactionvessel equipped with a stirrer, thermometer, condenser, dlopping funnel,and nitrogen gas inlet, after which 40 parts of "EMULGEN 950"(commercial name of poly(oxyethylene)nonylphenyl ether manufactured byKao Corp.) was added. The emulsifying agent was then dissolved byraising the temperature to 80° C. as the mixture was stirred andnitrogen gas was introduced into the reaction vessel.

5 parts of ammonium persulfate was then added, after which a mixtureconsisting of 500 parts of methyl methacrylate, 470 parts of n-butylacrylate, 30 parts of N,N-dimethylaminoethyl methacrylate, and 1.0 partof n-dodecyl mercaptan was added dropwise over 3 hours, to carry out thepolymerization reaction. Following completion of the drop addition, themixture was maintained at 80° C. for 2 hours while stirring wascontinued.

Next, the contents of the vessel were cooled, after which ammonia waterwas added to adjust the pH to in excess of 8. Deionized water was thenadded so that the concentration of the solid content was 40.0%, afterwhich the mixture was filtered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of40.0%, a pH of 8.1, and a viscosity of 80 cps according to a BMviscometer at 25° C. (same hereinafter). In addition, the aggregatewhich did not pass through the 100 mesh wire gauze was 0.1 or less(ratio relative to water dispersed solution). Hereinafter, this emulsionpolymer will be referred to as A-1.

Reference Example 2

[Preparation of an emulsion polymer (A) containing tertiary aminogroups]

Deionized water in the amount of 1,500 parts was added to a reactionvessel of the same type as employed in reference example 1, after which40 parts of "EMULGEN 950" was added. The emulsifying agent was thendissolved by raising the temperature to 80° C. as the mixture wasstirred and nitrogen gas was introduced into the reaction vessel.

5 parts of ammonium persulfate was then added, after which a mixtureconsisting of 500 parts of cyclohexyl methacrylate, 370 parts of2-ethylhexyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 10 partsof acrylic acid, 20 parts of N,N-dimethylaminoethyl methacrylate, and1.0 parts of n-dodecyl mercaptan was added dropwise over 3 hours, tocarry out the polymerization reaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 2 hours while stirring was continued. The contents of thevessel were then cooled, and deionized water was added until theconcentration of the solid content was 40.0%. The mixture was thenfiltered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of40.0%, a pH of 5.2, and a viscosity of 10 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.127 moles of tertiary amino group and 0.139 moles of carboxylgroup per 1,000 grams of solid content thereof. Hereinafter, thisemulsion polymer will be referred to as A-2.

Reference Example 3

[Preparation of emulsion polymer (A) containing tertiary amino groups]

Deionized water in the amount of 1,500 parts was added to a reactionvessel of the same type as employed in reference example 1, after which40 parts of "EMULGEN 950" was added. The emulsifying agent was thendissolved by raising the temperature to 80° C. as the mixture wasstirred and nitrogen gas was introduced into the reaction vessel.

5 parts of ammonium persulfate was then added, after which a mixtureconsisting of 500 parts of methyl methacrylate, 470 parts of n-butylacrylate, 10 parts of acrylic acid, 20 parts of N,N-dimethylaminoethylmethacrylate, and 1.0 part of n-dodecyl mercaptan was added dropwiseover 3 hours, to carry out the polymerization reaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 2 hours while stirring was continued. Next, the contents ofthe vessel were cooled, after which ammonia water was added to adjustthe pH to in excess of 8. Deionized water was then added so that theconcentration of the solid content was 40.0%, after which the mixturewas filtered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of40.0%, a pH of 8.1, and a viscosity of 80 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.127 moles tertiary amino group and 0.139 moles carboxyl groupper 1,000 grams of solid content thereof. Hereinafter, this emulsionpolymer will be referred to as A-3.

Reference Example 4

[Preparation of emulsion polymer (A) containing tertiary amino groups]

Deionized water in the amount of 1,500 parts was added to a reactionvessel of the same type as employed in reference example 1, after which40 parts of "EMULGEN 950" was added. The emulsifying agent was thendissolved by raising the temperature to 80° C. as the mixture wasstirred and nitrogen gas was introduced into the reaction vessel.

5 parts of ammonium persulfate was then added, after which a mixtureconsisting of 450 parts of cyclohexyl methacrylate, 370 parts of2-ethylhexyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 50 partsof 2-hydroxy ethyl acrylate, 10 parts of acrylic acid, 20 parts ofN,N-dimethylaminoethyl methacrylate, and 1.0 part of n-dodecyl mercaptanwas added dropwise over 3 hours, to carry out the polymerizationreaction. Following completion of the drop addition, the mixture wasmaintained at 80° C. for 2 hours while stirring was continued.

Next, the contents of the vessel were cooled, after which ammonia waterwas added to adjust the pH to 8.5. Deionized water was then added sothat the concentration of the solid content was 40.0%, after which themixture was filtered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of40.0%, a pH of 8.3, and a viscosity of 50 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.127 moles of tertiary amino group and 0.139 moles of carboxylgroup per 1,000 grams of solid content thereof. Hereinafter, thisemulsion polymer will be referred to as A-4.

Reference Example 5

[Preparation of emulsion polymer (A) containing tertiary amino groups]

Deionized water in the amount of 1,500 parts was added to a reactionvessel of the same type as employed in reference example 1, after which40 parts of "EMULGEN 950" was added. The emulsifying agent was thendissolved by raising the temperature to 80° C. as the mixture wasstirred and nitrogen gas was introduced into the reaction vessel.

5 parts of ammonium persulfate was then added, after which a mixtureconsisting of 499 parts of cyclohexyl methacrylate, 370 parts of2-ethylhexyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 10 partsof acrylic acid, 20 parts of N,N-dimethylaminoethyl methacrylate, and1.0 parts of γ-methacryloyloxypropyltrimethoxy silane, and 1.0 parts ofn-dodecyl mercaptan was added dropwise over 3 hours, to carry out thepolymerization reaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 2 hours while stirring was continued. Next, the contents ofthe vessel were cooled, after which ammonia water was added to adjustthe pH to in excess of 8. Deionized water was then added so that theconcentration of the solid content was 40.0%, after which the mixturewas filtered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of40.0%, a pH of 8.3, and a viscosity of 63 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.127 moles of tertiary amino group and 0.139 moles of carboxylgroup per 1,000 grams of solid content thereof. Hereinafter, thisemulsion polymer will be referred to as A-5.

Reference Example 6

[Preparation of emulsion polymer (A) containing tertiary amino groups]

Deionized water in the amount of 1,500 parts was added to a reactionvessel of the same type as employed in reference example 1, after which40 parts of "EMULGEN 950" was added. The emulsifying agent was thendissolved by raising the temperature to 80° C. as the mixture wasstirred and nitrogen gas was introduced into the reaction vessel.

5 parts of azobis(amidinopropane dihydrochloride) was then added, afterwhich a mixture consisting of 449 parts of cyclohexyl methacrylate, 370parts of 2-ethylhexyl methacrylate, 100 parts of 2-ethylhexyl acrylate,10 parts of acrylic acid, 20 parts of N,N-dimethylaminoethylmethacrylate, and 1.0 parts of γ-methacryloyloxypropyltrimethoxy silane,50 parts of 2-hydroxyethyl methacrylate and 1.0 parts of n-dodecylmercaptan was added dropwise over 3 hours, to carry out thepolymerization reaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 2 hours while stirring was continued. Next, the contents ofthe vessel were cooled, after which ammonia water was added to adjustthe pH to in excess of 8. Deionized water was then added so that theconcentration of the solid content was 40.0%, after which the mixturewas filtered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of40.0, a pH of 8.3, and a viscosity of 28 cps. In addition, the aggregatewhich did not pass through the 100 mesh wire gauze was 0.1% or less(ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.127 moles of tertiary amino group, 0.139 moles of carboxylgroup, and 0.385 moles of hydroxyl group per 1,000 grams of solidcontent thereof. Hereinafter, this emulsion polymer will be referred toas A-6.

Reference Example 7

[Preparation of a resin (anionic water soluble acrylic resin) for use asdispersion stabilizer]

Deionized water in the amount of 3,000 parts was added to a reactionvessel of the same type as employed in reference example 1, after which20 parts of "LEVENOL WZ" (commercial name of sodiumpoly(oxyethylene)alkylphenyl ether sulfonic acid, manufactured by KaoCorp., solid content: 25%) was added. The emulsifying agent was thendissolved by raising the temperature to 80° C. as the mixture wasstirred and nitrogen gas was introduced into the reaction vessel.

5 parts of ammonium persulfate was then added, after which a mixtureconsisting of 300 parts of methyl methacrylate, 549 parts of n-butylacrylate, 150 parts of methacrylic acid, 1.0 parts of mono2-methacryloxyethyl maleate, and 1.0 parts of n-dodecyl mercaptan wasadded dropwise over 3 hours, to carry out the polymerization reaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 1 hour while stirring was continued. Next, the contents ofthe vessel were cooled, after which deionized water was added so thatthe concentration of the solid content was 20.0%. The mixture was thenfiltered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of20.0%, a pH of 2.3, and a viscosity of 10 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution). Hereinafter, thisresin for use as a dispersive agent will be referred to as S-1.

Reference Example 8

[Preparation of a resin (anionic water soluble acrylic resin) for use asdispersion stabilizer]

Deionized water in the amount of 3,000 parts was added to a reactionvessel of the same type as employed in reference example 1, after which20 parts of "LEVENOL WZ" (solid content: 5 parts) was added. Theemulsifying agent was then dissolved by raising the temperature to 80°C. as the mixture was stirred and nitrogen gas was introduced into thereaction vessel.

5 parts of ammonium persulfate was then added, after which a mixtureconsisting of 300 parts of methyl methacrylate, 500 parts of n-butylacrylate, 150 parts of methacrylic acid, 49 parts of 2-hydroxyethylmethacrylate, 1.0 parts of γ-methacryloyloxypropyl trimethoxy silane,1.0 parts of n-dodecyl mercaptan was added dropwise over 3 hours, tocarry out the polymerization reaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 1 hour while stirring was continued. Next, the contents ofthe vessel were cooled, after which deionized water was added so thatthe concentration of the solid content was 20.0%. The mixture was thenfiltered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of20.0%, a pH of 2.4, and a viscosity of 10 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution). Hereinafter, thisresin for use as a dispersive agent will be referred to as S-2.

Reference Example 9

[Preparation of a resin (anionic water soluble acrylic resin) for use asdispersion stabilizer]

660 parts of ethylene glycol monoisopropyl ether was placed in areaction vessel of the same type employed in reference example 1. Next,as the monomer component, 50 parts of styrene, 100 parts of methylmethacrylate, 480 parts of n-butyl methacrylate, 150 parts of ethylacrylate, 50 parts of 2-hydroxyethyl methacrylate, 20 parts ofdimethylaminoethyl methacrylate, and 150 parts of methacrylic acid, and,as a radical polymerization initiator, 8 parts ofazobis(isobutyronitrile) and 5 parts of tert-butylperoxy octoate (TBPO),were dropped in over a period of 4 hours.

On completion of this addition, the temperature was maintained for afurther 10 hours. The targeted resin for use as a dispersion stabilizerwhich was obtained as a result had an average molecular weight of 9,500with a non-volatile content of 60%. Heteafter this polymer will bereferred to as S-3.

Reference Example 10

[Preparation of a resin (anionic water soluble acrylic resin) for use asdispersion stabilizer]

660 parts of ethylene glycol monoisopropyl ether was placed in areaction vessel of the same type employed in reference example 1. Next,a mixture comprising 50 parts of styrene, 100 parts of methylmethacrylate, 480 parts of n-butyl methacrylate, 150 parts of ethylacrylate, 50 parts of 2-hydroxyethyl methacrylate, 70 parts ofγ-methacryloyloxypropylmethyldimethoxysilane, 150 parts of methacrylicacid, 8 parts of azobis(isobutyronitrile) and 5 parts of TBPO, was addeddropwise over four hours.

On completion of this addition, the temperature was maintained for afurther 10 hours. The targeted resin for use as a dispersion stabilizerwhich was obtained as a result had an average molecular weight of 10,500with a non-volatile content of 60%. Hereafter this polymer will bereferred to as S-4.

Reference Example 11

[Preparation of emulsion polymer (A) containing tertiary amino groups]

Deionized water in the amount of 400 parts and resin (S-1) obtained inreference example 7 for use as a dispersion stabilizer in the amount of1,000 parts (solid content: 200 parts) were placed in a reaction vesselof the same type as employed in reference example 1. Thereafter, amixture comprising 12 parts of 28% ammonia water and 160 parts ofdeionized water was added over 1 hour. The pH was then adjusted to 6,and the temperature was raised to 80° C.

0.4 parts of ammonium persulfate was then added as stirring wascontinued. A mixture consisting of 80 parts of styrene, 281.5 parts ofcyclohexyl methacrylate, 320 parts of 2-ethylhexyl methacrylate, 80parts of ethylhexyl acrylate, 37.5 parts of N,N-dimethylaminoethylmethacrylate, and 1.0 parts of n-dodecyl mercaptan, was added dropwiseover 3 hours, to carry out the polymerization reaction.

After completion of this addition, the temperature was maintained for 1hour as stirring was continued.

The vessel contents were then cooled, after which deionized water wasadded so that the concentration of the solid content was 40.0%. The thusobtained emulsion polymer had a pH of 6.0 and a viscosity of 30 cps. Theaggregate which did not pass through the 100 mesh wire gauze was 4%,(ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.191 moles tertiary amino group and 0.358 moles carboxyl groupper 1,000 grams of solid content thereof. Hereinafter, this emulsionpolymer will be referred to as A-7.

Reference Example 12

[Preparation of emulsion polymer (A) containing tertiary amino groups]

Deionized water in the amount of 400 parts and resin (S-2) for use as adispersion stabilizer obtained in reference example 8 in the amount of1,000 parts (solid content: 200 parts) were placed in a reacLion vesselof the same type as employed in reference example 1. Thereafter, amixture comprising 12 parts of 28% ammonia water and 160 parts ofdeionized water was added over 1 hour. The pH was then adjusted to 6,and the temperature was raised to 80° C.

0.4 parts of ammonium persulfate was then added as stirring wascontinued. A mixture consisting of 79 parts of styrene, 281.5 parts ofcyclohexyl methacrylate, 320 parts of 2-ethylhexyl methacrylate, 80parts of 2-ethylhexyl acrylate, 37.5 parts of N,N-dimethylaminoethylmethacrylate, 1.0 parts of γ-methacryloyl oxypropyltrimethoxysilane, and1.0 parts of n-dodecyl mercaptan, were added dropwise over 3 hours, tocarry out the polymerization reaction. After completion of thisaddition, the temperature was maintained for 1 hour as stirring wascontinued.

The vessel contents were then cooled, after which deionized water wasadded so that the concentration of the solid content was 40.0%. The thusobtained emulsion polymer had a pH of 6.0 and a viscosity of 60 cps. Theaggregate which did not pass through the 100 mesh wire gauze was 4%(ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.191 moles of tertiary amino group and 0.349 moles of carboxylgroup per 1,000 grams of solid content thereof. Hereinafter, thisemulsion polymer will be referred to as A-8.

Reference Example 13

[Preparation of emulsion polymer (A) containing tetiary amino groups]

Resin (S-3) for use as a dispersion stabilizer obtained in referenceexample 9 in the amount of 333.3 parts (solid content: 200 parts) wasplaced in a reaction vessel of the same type as employed in referenceexample 1. Triethylamine was then added in the amount of 35.2 parts,after which 1,031.5 parts of deionized water was added over 1 hour. Thetemperature was then raised to 80° C.

0.4 parts of ammonium persulfate was then added as stirring wascontinued. A mixture consisting of 79 parts of styrene, 281.5 parts ofcyclohexyl methacrylate, 320 parts of 2-ethylhexyl methacrylate, 80parts of 2-ethylhexyl acrylate, 37.5 parts of N,N-dimethylaminoethylmethacrylate, 1.0 parts of γ-methacryloyloxypropyltrimethoxysilane, and1.0 parts of n-dodecyl mercaptan, was added dropwise over 3 hours, tocarry out the polymerization reaction. After completion of thisaddition, the temperature was maintained for 1 hour as stirring wascontinued.

The vessel contents were then cooled, after which deionized water wasadded so that the concentration of the solid content was 40.0%. Themixture was then filtered through a 100 mesh wire gauze. The thusobtained emulsion polymer had a pH of 9.9 and a viscosity of 160 cps.The aggregate which did not pass through the 100 mesh wire gauze was 4%(ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.264 moles of tertiary amino group and 0.349 moles carboxylgroup per 1,000 grams of solid content thereof. Hereinafter, hisemulsion polymer will be referred to as A-9.

Reference Example 14

[Preparation of emulsion polymer (A) containing tertiary amino groups]

Resin (S-4) for use as a dispersion stabilizer obtained in referenceexample 10 in the amount of 333.3 parts (solid content: 200 parts) wasplaced in a reaction vessel of the same type as employed in referenceexample 1. Triethylamine was then added in the amount of 35.2 parts,after which 1,031.5 parts of deionized water was added over 1 hour. Thetemperature was then raised to 80° C.

0.4 parts of ammonium persulfate was then added as stirring wascontinued. A mixture consisting of 79 parts of styrene, 281.5 parts ofcyclohexyl methacrylate, 320 parts of 2-ethylhexyl methacrylate, 80parts of 2-ethylhexyl acrylate, 37.5 parts of N,N-dimethylaminoethylmethacrylate, 1.0 parts of γ-methacryloyloxypropyltrimethoxysilane, and1.0 parts of n-dodecyl mercaptan, was added dropwise over 3 hours, tocarry out the polymerization reaction. After completion of thisaddition, the temperature was maintained for 1 hour as stirring wascontinued.

The vessel contents were then cooled, after which deionized water wasadded so that the concentration of the solid content was 40.0%. Themixture was then filtered through a 100 mesh wire gauze. The thusobtained emulsion polymer had a pH of 9.4 and a viscosity of 160 cps.The aggregate which did not pass through the 100 mesh wire gauze was 4%(ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.238 moles of tertiary amino group and 0.349 moles of carboxylgroup per 1,000 grams of solid content thereof. Hereinafter, thisemulsion polymer will be referred to as A-10.

Reference Examiple 15

[Preparation of emulsion polymer (A) containing tertiary amino groups]

Deionized water in the amount of 1,500 parts was added to a reactionvessel of the same type as employed in reference example 1, after which5 parts of "EMULGEN 950" was added as an emulsifying agent. Theemulsifying agent was then dissolved by raising the temperature to 80°C. as the mixture was stirred and nitrogen gas was introduced into thereaction vessel.

5 parts of ammonium persulfate was then added, after which a mixtureconsisting of 440 parts of methyl methacrylate, 470 parts of n-butylacrylate, 20 parts of acrylic acid, 20 parts of N,N-dimethyl aminoethylmethacrylate, 20 parts of "PME-200" (commercial name of a monomercontaining polyether chains, manufactured by NOF Corp.), 20 parts of"ELEMINOL JS-2", 1.0 parts of n-dodecyl mercaptan, and 2 parts of 25%ammonia water, was added dropwise over 3 hours, to carry out thepolymerization reaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 2 hours while stirring was continued. Next, the contents ofthe vessel were cooled, after which ammonia water was added to adjustthe pH to in excess of 8. Deionized water was then added so that theconcentration of the solid content was 40.0%, after which the mixturewas filtered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer has a solid content concentration of40.0%, a pH of 8.1 and a viscosity of 80 cps. Further, the aggregatewhich did not pass through the 100 mesh wire gauze was 0.1% or less(ratio relative to water dispersed solution).

This emulsion polymer containing a tertiary amino group was determinedto contain 0.127 moles of tertiary amino group and 0.278 moles ofcarboxyl group per 1,000 grams of solid content thereof. Hereinafter,this emulsion polymer will be referred to as A-11.

Reference Example 16 Preparation of Pigment Paste

200.8 parts of "TIPAQUE R-930" (commercial name of titanium oxideproduced by Ishihara Sangyo Co., Ltd.), "OROTAN SG-1" (commercial nameof a pigment disperser produced by the U.S. company Rohm & Haas Co.);3.9 parts of a 10% water soluble solution of sodium tripolyphosphate,1.8 parts of "NOIGEN EA-120" (commercial name of apoly(oxyethylene)nonylphenyl ether-based emulsifying agent produced byDai-ichi Kogyo Seiyaku Co., Ltd.), 14.5 parts of ethylene glycol, 0.8parts of "BESTSIDE FX" (commercial name of an anticorrosive agentproduced by Dainippon Ink & Chemicals, Inc.), 0.6 parts of "SN DEFOAMER121" (commercial name of a defoaming agent produced by SAN NOPCOLIMITED), 59.1 parts of deionized water, and 0.4 parts of 28%, ammoniawater were mixed together and stirred sufficiently at room temperatureusing a disper. The thus-obtained paste will be referred to as "pigmentpaste" hereinafter.

Working Examples 1˜13, and Comparative Example 1

A variety of white paints were prepared using conventional methods, atthe proportions shown in Table 1.

Next, using a 6 mil applicator, each of the paints was applied to asteel panel which had already been painted with a primer, constituted ofan oil-free alkyd resin and melamine resin, and then baked (i.e.,prepainted panel); a slate panel; and a polypropylene panel; and thenleft to dry at room temperature for 7 days to obtain a fully curedcoating film.

The coating film applied to the polypropylene panel was peeled from asubstrate and its gelling coefficient was measured. Meanwhile, thecoating film applied to the prepainted steel panel was evaluated forinitial gloss value, pencil hardness, and resistance to solvents, acids,alkalis and yellowing due to heat, and was also evaluated for resistanceto weathering and staining after exposure for a period of two years inthe suburbs of Miyazaki city.

Further, an evaluation was made on tests of secondary adhesiveproperties of the coating applied to the slate. These results are shownin Table 1.

                  TABLE 1                                                         ______________________________________                                                Working                                                                              Working   Working   Working                                      example 1 example 2 example 3 example 4                                     ______________________________________                                        PAINT COMPOSITION                                                               A-1         100                                                               A-2  100                                                                      A-3   100                                                                     A-4    100                                                                    Pigment paste 30.8 30.8 30.8 30.8                                             γ-GPTMS 2.7 3.8 3.8 3.8                                                 DBTDL 0.04 0.03 0.04 0.03                                                     NMP 0.4 0.4 0.4 0.4                                                           TEXANOL 0.4 0.4 0.4 0.4                                                       Paint name CC01 CC02 CC03 CC04                                              PAINT SURFACE                                                                   PROPERTIES                                                                    Paint name  CC01     CC02    CC03    CC04                                     Gelling 92 85 96 92                                                           coefficient (%)                                                               Initial gloss 80 74 85 80                                                     (20° C.)                                                               Pencil hardness B 2B HB HB                                                    Gloss retention 65 72 67 76                                                   coefficient (%)                                                               Solvent ⊚ Δ ⊚ ⊚                                                  resistance                            Resistance to                                                                           GOOD                                                                  acidity                                                                       Resistance to GOOD                                                            alkalinity                                                                  Secondary 70       100       30      100                                        adhesiveness                                                                  Resistance to 1.4 0.2 0.1 0.4                                                 yellowing due to                                                              heat (Δb)                                                             ______________________________________                                         Notes to Table 1:                                                             GPTMS . . . abbreviation for glycidoxypropyltrimethoxy silane                 DBTDL . . . abbreviation for dibutyl tin dilaurate                            NMP . . . abbreviation for Nmethyl pyrollidone                                TEXANOL . . . 2,2,4trimethyl-1,3-pentane diol monoisobutyl ester              Gelling coefficient (%): This percentage is calculated by dividing the        weight of the paint film after it has been separated from the material an     then soaked in acetone for 24 hours and dried, by the weight of film prio     to soaking in acetone, and then multiplying by 100.                           Pencil hardness: This refers to the hardness of a "Mitsubishi Uni" pencil     [brand name, produced by Mitsubishi Pencil Co., Ltd.] required to scratch     the coating film.                                                             Gloss retention coefficient (%): This percentage value is calculated by       the prepared below. The higher this value, the greater the weather            resistant properties of the coating film.                                     Gloss retention coefficient (%) = G.sub.1 /G.sub.0 × 100                (Where, in this prepared G.sub.1 refers to the 60° gloss value (th     percentage of 60° incident light reflected) after 1 year exposure      to the elements, and G.sub.0 refers to the initial 60° gloss           value.)                                                                       Solvent resistance: A piece of felt soaked in methyl ethyl ketone was         placed on a sample of the paint film and weighted down with a 500 g           weight. The felt was then rubbed back and forth over the paint surface 10     times and a visual evaluation was made of the external appearance of the      coating film. The evaluation standards used are as follows.                   ⊚ no change                                                    ∘ slight scratches visible                                        Δ marked loss in surface gloss                                          X dissolution and loss of coating film                                        Resistance to acidity: A 5% aqueous solution of sulfuric acid was dropped     on to the film for a period of 24 hours, and the film then washed with        water, and its external appearance evaluated visually.                        Resistance to alkalinity: A 5% aqueous solution of sodium hydroxide was       dropped on to the film for a period of 24 hours, and the film then washed     with water, and its external appearance evaluated visually.                   Secondary adhesiveness: A sample of the paint film was soaked in warm         water at 40° C. for a period of one week. Following soaking, a         cross cut pattern, consisting of 11 horizontal and 11 vertical cuts at        regular intervals, was made on the film's surface and a stripping test        carried out using cellophane tape. This was then employed as one              evaluation of water resistance.                                               Resistance to yellowing due to heat: A paint film, cured for 7 days at        room temperature, was over baked at 80° C. for a period of one         hour, at which point the yellowing of the film was measured. The value [b     refers to the difference between the measured value and that for yellowin     prior to over baking.                                                    

    Working        Working   Working   Working                                      example 5 example 6 example 7 example 8                                     ______________________________________                                        PAINT COMPOSITION                                                               A-4         100      100                                                      A-5   100                                                                     A-6    100                                                                    Pigment paste 30.8 30.8 30.8 30.8                                             UV absorption 0.8 0.8 0.8 0.8                                                 agent                                                                         γ-GPTMS 2.5 3.8 3.8 3.8                                                 TSL 2.0 2.0 2.0 2.0                                                           N-MP 0.4 0.4 0.4 0.4                                                          TEXANOL 0.4 0.4 0.4 0.4                                                       Paint name CC05 CC06 CC07 CC08                                              PAINT SURFACE                                                                   PROPERTIES                                                                    Paint name  CC05     CC06    CC07    CC08                                     Gelling 89 92 96 88                                                           coefficient (%)                                                               Initial gloss 20° 82 78 72 78                                          Pencil hardness 3B H F 2B                                                     Gloss retention 78 84 88 89                                                   coefficient (%)                                                               Solvent Δ ◯ ◯ ⊚                  resistance                                                                  Resistance to                                                                           GOOD                                                                  acidity                                                                       Resistance to GOOD                                                            alkalinity                                                                  Secondary 75       90        100     100                                        adhesiveness                                                                  Resistance to 0.1 0.1 0.1 0.1                                                 yellowing due to                                                              heat (Δb)                                                             ______________________________________                                         Notes to Table 1:                                                             UV absorption agent . . . mixture in a 1:1 weight ratio of "TINUBIN 123"      and "TINUBIN 384", both manufactured by the Swiss company CibaGeigy Corp.     TSL . . . abbreviation for a 2:1 blended mixture of "TSL 8178" and "TSL       8122", both silicate compounds manufactured by Toshiba Silicone Co., Ltd.

    Working        Working   Working   Working                                      example 9 example 10 example 11 example 12                                  ______________________________________                                        PAINT COMPOSITION                                                               A-7         100                                                               A-8  100                                                                      A-9   100                                                                     A-10    100                                                                   Pigment paste 30.8 30.8 30.8 30.8                                             UV absorption 0.8 0.8 0.8 0.8                                                 agent                                                                         γ-GPTMS 7.8 7.6                                                         γ-GPMDMS   8.1 7.7                                                      DBTDL 0.04                                                                    SH-6018 2.0 2.0 2.0 2.0                                                       Paint name CC09 CC10 CC11 CC12                                              PAINT SURFACE                                                                   PROPERTIES                                                                    Paint name  CC09     CC10    CC11    CC12                                     Gelling 95 94 94 90                                                           coefficient (%)                                                               Initial gloss 20° 72 78 82 78                                          Pencil hardness 2B 2B HB B                                                    Gloss retention 84 89 79 76                                                   coefficient (%)                                                               Solvent ◯ ◯ ◯ ◯                                                     resistance                            Resistance to                                                                           GOOD                                                                  acidity                                                                       Resistance to GOOD                                                            alkalinity                                                                  Secondary 100      100       100     100                                        adhesiveness                                                                  Resistance to 0.3 0.3 0.1 0.1                                                 yellowing due to                                                              heat (Δb)                                                             ______________________________________                                         Notes to Table 1                                                              GPMDMS . . . abbreviation for glycidoxypropylmethyldimethoxysilane.           SH6018 . . . Abbreviation for "Toray Silicone SH6018", a silicone compoun     produced by Toray Silicone Co., Ltd.                                     

                   Working      Comparative                                          example 13 example 1                                                       ______________________________________                                          PAINT COMPOSITION                                                             A-11 100                                                                      A-1  100                                                                      Pigment paste 30.8 30.8                                                       γ-GPTMS 3.8 0                                                           DBTDL 0.04                                                                    NMP 0.4 0.4                                                                   TEXANOL 0.4 0.4                                                               Paint name CC13 CC'01                                                         PAINT SURFACE                                                                 PROPERTIES                                                                    Paint name CC13 CC'01                                                         Gelling 83 0                                                                  coefficient (%)                                                               Pencil hardness 2B 5B                                                         Gloss retention 60 5.8                                                        coefficient (%)                                                               Solvent Δ X                                                             resistance                                                                    Resistance to GOOD Deterioration                                              acidity  in gloss                                                             Resistance to GOOD Film break-up                                              alkalinity                                                                    Secondary 70 0                                                                adhesiveness                                                                  Resistance to 0.2 2.3                                                         yellowing due to                                                              heat (Δb)                                                             ______________________________________                                    

Reference Example 17

[Preparation of emulsion polymer (A) containing tertiary amino groups]

Deionized water in the amount of 1,500 parts was added to a reactionvessel of the same type as employed in reference example 1, after which40 parts of "EMULGEN 950" was added. The emulsifying agent was thendissolved by raising the temperature to 80° C. as the mixture wasstirred and nitrogen gas was introduced into the reaction vessel.

5 parts of azobis(amidinopropane dihydrochloride) was then added, afterwhich a mixture consisting of 449 parts cyclohexyl methacrylate, 370parts of 2-ethylhexyl methacrylate, 100 parts of 2-ethylhexyl acrylate,10 parts of acrylic acid, 20 parts of N,N-dimethylaminoethylmethacrylate, 1.0 parts of γ-methacryloyloxypropyltrimethoxysilane, 5.0parts of 2-hydroxyethyl methacrylate, and 1 part of n-dodecyl mercaptanwas added dropwise over 3 hours, to carry out the polymerizationreaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 2 hours while stirring was continued. Next, the contents ofthe vessel were cooled, after which ammonia water was added to adjustthe pH to in excess of 8. Deionized water was then added so that theconcentration of the solid content was 40.0%, after which the mixturewas filtered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of40.0%, a pH of 8.3, and a viscosity of 28 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.127 moles of tertiary amino group, 0.139 moles of carboxylgroup, and 0.385 moles of hydroxyl group per 1,000 grams of solidcontent thereof. Hereinafter, this emulsion polymer will be referred toas A-12.

Reference Example 18

[Preparation of a resin (anionic water soluble acrylic resin) for use asdispersion stabilizer]

Deionized water in the amount of 3,000 parts was added to a reactionvessel of the same type as employed in reference example 1, after which20 parts (solid content: 5 parts) of "LEVENOL WZ" (commercial name ofsodium poly(oxyethylene)alkylphenyl ether sulfonic acid, produced by KaoCorp.; solid content: 25%) was added as an emulsifying agent. Theemulsifying agent was then dissolved by raising the temperature to 80°C. as the mixture was stirred and nitrogen gas was introduced into thereaction vessel.

5 parts of ammonium persulfate was then added, after which a mixtureconsisting of 305 parts of methyl methacrylate, 660 parts of n-butylacrylate, 30 parts of methacrylic acid, 5 parts of mono 2-methacryloxyethyl maleate, and 1.0 parts of n-dodecyl mercaptan was added dropwiseover 3 hours, to carry out the polymerization reaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 1 hour while stirring, was continued. Next, the contents ofthe vessel were cooled, after which deionized water was added so thatthe concentration of the solid content was 20.0%. The mixture was thenfiltered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of20.0%, a pH of 3.4, and a viscosity of 10 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution). Hereinafter, thisresin for use as a dispersive agent will be referred to as S-5.

Reference Example 19

[Preparation of a resin (anionic water soluble acrylic resin) for use asdispersion stabilizer]

Deionized water in the amount of 3,000 parts was placed in a reactionvessel of the same type employed in reference example 1, after which 20parts of "LEVENOL WZ" (solid content: 5 parts) was added as anemulsifying agent. Next, the emulsifying agent was melted by raising thetemperature to 80° C. as the mixture was stirred and nitrogen gas wasintroduced into the reaction vessel.

Next, 5 parts of ammonium persulfate was added, followed by the dropaddition over three hours of a monomer mixture consisting of 300 partsof methyl methacrylate, 600 parts of n-butyl acrylate, 50 parts ofmethacrylic acid, 49 parts of 2-hydroxy ethyl methacrylate, 1.0 part ofγ-methacryloyloxypropyltrimethoxysilane, and 1.0 parts of n-dodecylmercaptan.

Following completion of this addition, the mixture was maintained at 80°C. and stirred for one hour. Next, the contents of the vessel werecooled, after which deionized water was added so that the concentrationof the solid content was 20.0%. The mixture was then filtered through a100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of20.0%, a pH of 3.2, and a viscosity of 10 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution). Hereinafter, thisresin for use as a dispersive agent will be referred to as S-6.

Reference Example 20

[Preparation of a resin (anionic water soluble acrylic resin) for use asdispersion stabilizer]

660 parts of ethylene glycol monoisopropyl ether was placed in areaction vessel of the same type as employed in reference example 1.Next, a mixture comprising 50 parts of styrene, 100 parts of methylmethacrylate, 480 parts of n-butyl methacrylate, 220 parts of ethylacrylate, 50 parts of 2-hydroxyethyl methacrylate, 20 parts ofdimethylaminoethyl methacrylate, and 80 parts of methacrylic acid, asthe monomers, and 8 parts of azobis(isobutyronitrile) and 5 parts oftert-butylperoxy octoate (TBPO), as the radical polymerizationinitiators, was added dropwise over four hours.

On completion of this addition, the temperature was maintained for afurther 10 hours. The targeted resin for use as a dispersion stabilizerwhich was obtained as a result had an number-average molecular weight of9,500 with a non-volatile content of 60%. Hereinafter, this polymer willbe referred to as S-7.

Reference Example 21

[Preparation of emulsion polymer (A)]

Deionized water in the amount of 400 parts and resin (S-5) obtained inreference example 18 for use as a dispersion stabilizer in the amount of1,000 parts (solid content: 200 parts) were placed in a reaction vesselof the same type as employed in reference example 1. Thereafter, amixture comprising 12 parts of 28% ammonia water and 160 parts deionizedwater was added over 1 hour. The pH was then adjusted to 6, and thetemperature was raised to 80° C.

0.4 parts of ammonium persulfate was then added as stirring wascontinued. A mixture consisting of 80 parts of styrene, 281.5 parts ofcyclohexyl methacrylate, 320 parts of 2-ethylhexyl methacrylate, 80parts of 2-ethylhexyl acrylate, 37.5 parts of N,N-dimethylaminoethylmethacrylate, and 1.0 parts of n-dodecyl mercaptan, was added dropwiseover 3 hours, to carry out the polymerization reaction. After completionof this addition, the temperature was maintained for 1 hour as stirringwas continued.

The vessel contents were then cooled, after which deionized water wasadded so that the concentration of the solid content was 40.0%. The thusobtained emulsion polymer had a pH of 6.0 and a viscosity of 30 cps. Theaggregate which did not pass through the 100 mesh wire gauze was 4%(ratio relative to water dispersed solution).

This emulsion polymer containing tertiary amino groups was determined tocontain 0.191 moles of tertiary amino group and 0.358 moles of carboxylgroup per 1,000 grams of solid content thereof. Hereinafter, thisemulsion polymer will be referred to as A-13.

Reference Example 22

[Preparation of emulsion polymer (A)]

Deionized water in the amount of 400 parts and resin (S-6) obtained inreference example 19 for use as a dispersion stabilizer in the amount of1,000 parts (solid content: 200 parts) were placed in a reaction vesselof the same type as employed in reference example 1. Thereafter, amixture comprising 12 parts of 28% ammonia water and 160 parts ofdeionized water was added over 1 hour. The pH was then adjusted to 6,and the temperature was raised to 80° C.

0.4 parts of ammonium persulfate was then added as stirring wascontinued. A mixture consisting of 79 parts of styrene, 281.5 parts ofcyclohexyl methacrylate, 320 parts of 2-ethylhexyl methacrylate, 80parts 2-ethyl hexyl acrylate, 37.5 parts N,N-dimethyl aminoethylmethacrylate, 1.0 parts of γ-methacryloyloxypropyltrimethoxysilane and1.0 parts of n-dodecyl mercaptan, was added dropwise over 3 hours, tocarry out the polymerization reaction. After completion of thisaddition, the temperature was maintained for 1 hour as stirring wascontinued.

The vessel contents were then cooled, after which deionized water wasadded so that the concentration of the solid content was 40.0%. The thusobtained emulsion polymer had a pH of 6.0 and a viscosity of 60 cps. Theaggregate which did not pass through the 100 mesh wire gauze was 4%(ratio relative to water dispersed solution).

This emulsion polymer was determined to contain 0.191 moles tertiaryamino group and 0.349 moles of carboxyl group per 1,000 grams of solidcontent thereof. Hereinafter, this emulsion polymer will be referred toas A-14.

Reference Example 23

[Preparation of emulsion polymer (A)]

333.3parts (solidcontent: 200parts) of resin (S-7) obtained in referenceexample 20 for use as a dispersion stabilizer was placed in a reactionvessel of the same type as employed in reference example 1, after which35.2 parts of triethyl amine was added. Next, deionized water in theamount of 1,031.5 parts was added over the course of one hour. Thetemperature was then raised to 80° C.

Next, as stirring was continued, 0.4 parts of ammonia persulfate wasadded to the mixture, followed by adding dropwise over three hours of amixture comprising 79 parts of styrene, 281.5 parts of cyclohexylmethacrylate, 320 parts of 2-ethylhexyl methacrylate, 80 parts of2-ethylhexyl acrylate, 37.5 parts of N,N-dimethylaminoethylmethacrylate, 1.0 parts of γ-methacryloyloxypropyltrimethoxysilane and1.0 parts of n-dodecyl mercaptan, to carry out the polymerizationreaction. Following completion of this addition, the mixture wasmaintained at 80° C. while stirring was continued.

The vessel contents were then cooled, after which deionized water wasadded so that the concentration of the solid content was 40.0%. Themixture was then filtered through a 100 mesh wire gauze. The thusobtained emulsion polymer had a solid concentration of 40.0%, a pH of9.9 and a viscosity of 160 cps. The aggregate which did not pass throughthe 100 mesh wire gauze was 4% (ratio relative to water dispersedsolution).

This emulsion polymer was determined to contain 0.264 moles of tertiaryamino group and 0.349 moles of carboxyl group per 1,000 grams of solidcontent thereof. Hereinafter, this emulsion polymer will be referred toas A-15.

Reference Example 24

[Preparation of emulsion polymer (A)]

Deionized water in the amount of 1,500 parts was added to a reactionvessel of the same type as employed in reference example 1, after which5 parts of "EMULGEN 950" was added. The emulsifying agent was thendissolved by raising the temperature to 80° C. as the mixture wasstirred and nitrogen gas was introduced into the reaction vessel.

5 parts of ammonium persulfate was then added, after which a mixtureconsisting of 440 parts of methyl methacrylate, 470 parts of n-butylacrylate, 20 parts of acrylic acid, 20 parts of N,N-dimethylaminoethylmethacrylate, 20 parts of "PME-200" (commercial name of a monomercontaining polyether chains, manufactured by NOF Corp.), 20 parts of"ELEMINOL JS-2", 1.0 part of n-dodecyl mercaptan, and 2 parts of 25%ammonia water was added dropwise over 3 hours, to carry out thepolymerization reaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 2 hours while stirring was continued. Next, the contents ofthe vessel were cooled, after which ammonia water was added to adjustthe pH to in excess of 8. Deionized water was then added so that theconcentration of the solid content was 40.0%, after which the mixturewas filtered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of40.0%, a pH of 8.1, and a viscosity of 80 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution).

This emulsion polymer was determined to contain tertiary amino group inthe amount of 0.127 moles, and carboxyl group in the amount of 0.278moles, per 1,000 grams of solid content thereof. Hereinafter, thisemulsion polymer will be referred to as A-16.

Reference Example 25

[Preparation of emulsion polymer (A)]

Deionized water in the amount of 1,500 parts was added to a reactionvessel of the same type as employed in reference example 1, after which1.0 parts of "EMULGEN 950" was added. The emulsifying agent was thendissolved by raising the temperature to 80° C. as the mixture wasstirred and nitrogen gas was introduced into the reaction vessel.

1.0 parts of ammonium persulfate was then added, after which a mixtureconsisting of 170 parts of ethyl acrylate, 30 parts of methacrylic acid,2 parts of mono 2-methacryloxyethyl maleate, and 3 parts of 28% ammoniawater was added dropwise over 1 hour, to carry out the polymerizationreaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 30 minutes while stirring was continued. Next, 3 partsammonium persulfate was added, followed by the drop addition over threehours of a monomer mixture consisting of 50 parts styrene, 370 parts ofmethyl methacrylate, 348 parts of n-butyl acrylate, 30 parts ofN,N-dimethylaminoethyl methacrylate, and 1.0 parts of n-dodecylmercaptan.

After completion of this addition, the mixture was maintained at 80° C.for two hours while stirring was continued. Next, the contents of thevessel were cooled, after which ammonia water was added to adjust the pHto in excess of 8. Deionized water was then added so that theconcentration of the solid content was 40.0%, after which the mixturewas filtered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of40.0%, a pH of 8.1, and a viscosity of 80 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution).

This emulsion polymer was determined to contain tertiary amino group inthe amount of 0.191 moles, and carboxyl group in the amount of 0.349moles, per 1,000 grams of solid content thereof. Hereinafter, thisemulsion polymer will be referred to as A-17.

Reference Example 26

[Preparation of emulsion polymer (A)]

Deionized water in the amount of 1,500 parts was added to a reactionvessel of the same type as employed in reference example 1, after which10 parts of "EMULGEN 950" was added. The emulsifying agent was thendissolved by raising the temperature to 80° C. as the mixture wasstirred and nitrogen gas was introduced into the reaction vessel.

1 part of azobis(amidinopropane dihydrochloride) was then added, afterwhich a monomer mixture consisting of 150 parts of n-butyl acrylate, 120parts of methyl methacrylate, and 30 parts of N,N-dimethylaminoethylmethacrylate, and 20 parts of acetic acid, were added dropwise over 1hour, to carry out the polymerization reaction.

Following completion of the drop addition, the mixture was maintained at80° C. for 30 minutes while stirring was continued. Next, 3 parts oftert-butyl hydroperoxide and 1.5 parts of sodium prepared sulfoxylatedihydrate were added, followed by adding dropwise over three hours of amonomer mixture consisting of 240 parts of methyl methacrylate, 150parts of tert-butyl methacrylate, 300 parts of n-butyl acrylate, 4 partsof glycidyl methacrylate, and 1 part of n-dodecyl mercaptan.

After completion of this addition, the mixture was maintained at 80° C.for two hours while stirring was continued. Next, the contents of thevessel were cooled, after which deionized water was added to adjust theconcentration of the solid content to 40.0%. The mixture was thenfiltered through a 100 mesh wire gauze.

The thus-obtained emulsion polymer had a solid content concentration of40.0%, a pH of 5.6, and a viscosity of 580 cps. In addition, theaggregate which did not pass through the 100 mesh wire gauze was 0.1% orless (ratio relative to water dispersed solution).

This emulsion polymer was determined to contain tertiary amino group inthe amount of 0.191 moles per 1,000 grams of solid content thereof.Hereinafter, this emulsion polymer will be referred to as A-18.

Reference Example 27

[Preparation of vinyl polymer (I) containing acidic groups and/ortertiary amino groups]

660 parts of ethylene glycol monoisopropyl ether was placed in areaction vessel equipped with a stirrer, thermometer, condenser andnitrogen inlet, and the temperature was raised to 80° C. under anitrogen gas atmosphere.

Next, a mixture consisting of 100 parts of styrene, 200 parts of methylmethacrylate, 480 parts of n-butyl methacrylate, 70 parts of ethylacrylate, 50 parts of 2-hydroxyethyl methacrylate, 100 parts ofdimethylaminoethyl methacrylate, and 8 parts of azobis(isobutyronitrile)and 5 parts of tert-butylperoxy octoate (TBPO), was added dropwise overfour hours, to carry out polymerization.

On completion of this addition, the temperature was maintained for afurther 10 hours to obtain a solution of the targeted tertiary aminovinyl polymer (I) which had a number-average molecular weight of 9,500with a non-volatile content of 60%. Hereinafter, this polymer will bereferred to as (I-a).

Reference Example 28

[Preparation of water-based compound (C)]

2 parts of an 88% aqueous solution of formic acid was added to 100 partspolymer (I-a) obtained in reference example 27, with stirring continued.The neutralization rate in this case was 100%.

Next, 98 parts of water was added, with the mixture stirred untiluniform. The targeted water-based compound obtained had a non-volatilecomponent of 30%, with 0.637 moles of tertiary amino group contained inthis water-based compound per 1,000 grams of solid content thereof.Hereinafter, this water-based compound will be referred to as (C-1).

Reference Example 29

[Preparation of vinyl polymer (I) containing acidic groups and/ortertiary amino groups]

With the exception that a mixture consisting of 50 parts of styrene, 250parts of methyl methacrylate, 430 parts of n-butyl methacrylate, 150parts of ethyl acrylate, 50 parts of 2-hydroxy ethyl acrylate, 40 partsof dimethylaminoethyl methacrylate, and 30 parts methacrylic acid, wasemployed for the monomer mixture, and 10 parts TBPC) was employed forthe radical polymerization initiator, a solution of the targeted vinylpolymer (I) containing both tertiary amino groups and acidic groups wasobtained in the same manner as in reference example 27. This vinylpolymer (I) had a number-average molecular weight of 8,000 with anon-volatile content of 60%. Hereinafter, this polymer will be referredto as (I-b).

Reference Example 30

[Preparation of water-based compound (C)]

0.8 parts of an 88% aqueous solution of formic acid was added to 100parts polymer (I-b) obtained in reference example 29, with stirringcontinued.

Next, 49.2 parts water was added, with the mixture stirred untiluniform. The targeted water-based compound obtained had a non-volatilecontent of 40%, with 0.255 moles of tertiary amino group and 0.349 molesof carboxylic acid group contained in this water-based compound per1,000 grams of solid content thereof. Hereinafter, this water-basedcompound will be referred to as (C-2).

Reference Example 31

[Preparation of water-based compound (C)]

2.1 parts of triethyl amine was added to 100 parts of the vinyl polymer(I-b) obtained in reference example 29, with stirring continued.Thereafter, 47.9 parts of water was added, with the mixture then stirreduntil a uniform dispersion was obtained. The targeted water-basedcompound obtained had a non-volatile content of 40%.

The water-based compound contained 0.255 moles of tertiary amino groupand 0.349 moles of carboxyl group per 1,000 grams of solid contentthereof. Hereinafter, this water-based compound will be referred to as(C-3).

Reference Example 32

[Preparation of vinyl polymer (I) containing acidic groups and/ortertiary amino groups]

With the exception that 666 parts of ethylene glycol monoisopropyl etherwas employed as the polymerization solvent, a mixture consisting of 150parts of styrene, 500 parts of n-butyl methacrylate, 150 parts of ethylacrylate, 100 parts of 2-hydroxy ethyl acrylate, and 100 parts ofacrylic acid, was employed for the monomer mixture, and 10 parts of TBPOwas employed for the radical polymerization initiator, a solution of thetargeted vinyl polymer (III) containing acidic groups was obtained inthe same manner as in reference example 1. This vinyl polymer (III) hada number-average molecular weight of 8,000 with a non-volatile contentof 60%. Hereinafter, this polymer will be referred to as (I-c).

Reference Example 33

[Preparation of water-based compound (C)]

1.8 parts of N,N-dimethyloctyl amine and 2.2 parts of triethyl amine wasadded to 100 parts of polymer (I-c) obtained in reference example 32,with stirring carried out. Thereafter, 96 parts of water was added, withthe mixture stirred to form a uniform dispersion. The targetedwater-based compound obtained had a non-volatile component of 30%), with1.389 moles of carboxyl group contained in this water-based compound per1,000 grams of solid content thereof. Hereinafter, this water-basedcompound will be referred to as (C-4).

Working Examples 13 to 27 and Comparative Examples 2 to 6

A variety of white paints were prepared by mixing the variousconstituents in the ratios shown in Table 2. The paints were thendiluted with deionized water to a value of 85 KU as measured with astomer viscometer.

Next, using a 6 mil applicator, each of the paints was applied to asteel panel which had already been painted with a primer, constituted ofan oil free alkyd resin and melamine resin, and then baked (i.e., aprepainted panel); a slate panel; and a polypropylene panel; and thenleft to dry at ambient temperature for 7 days to obtain a fully curedcoating film.

The coating material was also applied to the prepainted panel using asagging tester, immediately after which the panel was stood upright, andsag of wet film thickness was evaluated.

For each of the cured coatings, the film applied to the polypropylenesheet was peeled from the panel and its gelling coefficient wasmeasured, while the coating film applied to the prepainted steel panelwas evaluated for initial gloss, pencil hardrness and resistance tosolvents, acids, alkalis, and yellowing due to heat, as well as forresistance to weathering after exposure for a period of two years, andresistance to staining after exposure for a period of one month, in thesuburbs of Miyazaki city.

In addition, an evaluation was made of secondary adhesion testsconducted on the coating applied to the slate. A summary of theseresults is shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                 Working                                                                              Working   Working  Working                                      example example example example                                               13 14 15 16                                                                 ______________________________________                                        PAINT COMPOSITION                                                               A-1          188                                                              A-3  188                                                                      A-4   188                                                                     A-12    188                                                                   C-3 62.5 62.5 62.5 62.5                                                       R-930 53.8 53.8 53.8 53.8                                                     γ-GPTMS 10.4 9.04 12.4 12.4                                             DBTDL 0.05 0.05 0.05 0.05                                                     NMP 1.0 1.0 1.0 1.0                                                           TEXANOL 1.0 1.0 1.0 1.0                                                       Paint name CC13 CC14 CC15 CC16                                                PAINT SURFACE                                                                 PROPTERTIES                                                                   Paint name CC13 CC14 CC15 CC16                                                Gelling 92 94 84 97                                                           coefficient (%)                                                               Initial gloss 80 79 72 74                                                     (20° C.)                                                               Pencil hardness B B HB HB                                                     Gloss retention 65 69 76 77                                                   coefficient (%)                                                               Solvent ⊚ ⊚ Δ ◯                                                     resistance                            Resistance to                                                                            GOOD                                                                 acidity                                                                       Resistance to GOOD                                                            alkalinity                                                                  Secondary  70       60        80     90                                         adhesiveness                                                                  Resistance to 1.4 0.2 0.1 0.4                                                 yellowing due to                                                              heat (Δb)                                                               Resistance to ◯ ◯ ◯ ◯                                             dirt shedding                           Critical wet film                                                                        329 μm or more                                                    thickness in sag                                                              resistance at                                                                 vertical plane                                                              ______________________________________                                         Notes to Table 2:                                                             R930 . . . abbreviation for "TIPAQUE R930", brand name of titanium oxide      produced by Ishihara Sangyo Co., Ltd.                                         GPTMS . . . abbreviation for glycidoxypropyltrimethoxysilane                  DBTDL . . . abbreviation for dibutyl tin dilaurate                            NMP . . . abbreviation for Nmethyl pyrrolidone                                TEXANOL . . . 2,2,4trimethyl-1,3-pentane diolmonoisobutyl ester               Gelling coefficient (%): This percentage is calculated by dividing the        weight of the paint film after it has been peeled from the material and       then soaked in acetone for 24 hours and dried, by the weight of film prio     to soaking in acetone, and then multiplying by 100.                           Pencil hardness: This refers to the hardness of a "Mitsubishi Uni" pencil     [brand name, produced by Mitsubishi Pencils Co., Ltd.] required to scratc     the coating film.                                                             Gloss retention coefficient (%): This percentage value is calculated by       the prepared below. The higher this value, the greater the weather            resistant properties of the coating film.                                     Gloss retention coefficient (%) = G.sub.1 /G.sub.0 × 100                (Where, in this prepared G.sub.1 refers to the 60° gloss value (th     percentage of 60° incident light reflected) after 1 year exposure      to the elements, and G.sub.0 refers to the initial 60° gloss           value.)                                                                       Solvent resistance: A piece of felt soaked in methyl ethyl ketone was         placed on a sample of the paint film and weighted down with a 500 g           weight. The felt was then rubbed back and forth over the paint surface 10     times and a visual evaluation was made of the external appearance of the      coating film. The evaluation standards used are as follows.                   ⊚ no change                                                    ∘ slight scratches visible                                        Δ marked loss in surface gloss                                          X dissolution and loss of coating film                                        Resistance to acidity: A 5% aqueous solution of sulfuric acid was dropped     on to the film for a period of 24 hours, and the film then washed with        water, and its external appearance evaluated visually.                        Resistance to alkalinity: A 5% aqueous solution of sodium hydroxide was       dropped on to the film for a period of 24 hours, and the film then washed     with water, and its external appearance evaluated visually.                   μm: Indicates from micrometers or microns.                                 Secondary adhesiveness: A sample of the paint film was soaked in warm         water at 40° C. for a period of one week. Following soaking, a         cross cut pattern, consisting of 11 horizontal and 11 vertical cuts at        regular intervals, was made on the film's surface and a stripping test        carried out using cellophane tape. This was then employed as one              evaluation of water resistance.                                               Resistance to yellowing due to heat: A paint film, cured for 7 days at        room temperature, was over baked at 80° C. for a period of one         hour, at which point the yellowing of the film was measured. The value [b     refers to the difference between the measured value and that for yellowin     prior to over baking. This has been indicated as [Δb].                  Resistance to dirt shedding . . . A visual evaluation was made of stainin     to the film after exposure for one month during which rain was allowed to     drop onto the film.                                                           ⊚ . . . almost no staining                                     ◯ . . . slight staining over the entire film, but could be        wiped away with gauze dampened in water                                       Δ . . . striated staining observed, but could be wiped away with        gauze dampened in water                                                       X . . . marked striated staining, which could not be wiped away with gauz     dampened in water                                                        

    Working            Working    Working                                           example 17 example 18 example 19                                            ______________________________________                                        PAINT COMPOSITION                                                               A-13          188                                                             A-14  188                                                                     A-15   188                                                                    C-3 62.5  62.5                                                                C-4  83.3                                                                     R-930 53.8 53.8 53.8                                                          UV absorption 2.0 2.0 2.0                                                     agent                                                                         γ-GPTMS 19.9 17.6 21.6                                                  TSL 15.0 15.0 15.0                                                            NMP 1.0 1.0 1.0                                                               TEXANOL 1.0 1.0 1.0                                                           Paint name CC17 CC18 CC19                                                   PAINT SURFACE                                                                   PROPERTIES                                                                    Paint name    CC17       CC18     CC19                                        Gelling 88 96 94                                                              coefficient (%)                                                               Initial gloss 20° 72 79 78                                             Pencil hardness H F F                                                         Gloss retention 87 89 80                                                      coefficient (%)                                                               Solvent ◯ ◯ ◯                             resistance                                                                  Resistance to                                                                             GOOD                                                                acidity                                                                       Resistance to GOOD                                                            alkalinity                                                                  Secondary   100        100        100                                           adhesiveness                                                                  Resistance to 0.1 0.1 0.1                                                     yellowing due to                                                              heat (Δb)                                                               Resistance to ⊚ ⊚ ⊚                                               dirt shedding                              Critical wet film                                                                         329 μm or greater                                                thickness in sag                                                              resistance test                                                               at vertical plane                                                           ______________________________________                                         Notes to Table 2:                                                             Numbers in the table indicate parts by weight.                                UV absorption agent . . . mixture in a 1:1 weight ratio of "TINUBIN 123"      and "TINUBIN 384", both manufactured by the Swiss company CibaGeigy Corp.     TSL . . . abbreviation for a 2:1 blended mixture of "TSL 8178" and "TSL       8122", both silicate compounds manufactured by Toshiba Silicone Co., Ltd.

               Working  Working   Working                                                                              Working                                     example example example example                                               20 21 22 23                                                                ______________________________________                                          PAINT SURFACE                                                                 PROPERTIES                                                                    A-16 188                                                                      A-17  188                                                                     A-18   188 188                                                                C-1   83.3                                                                    C-2    62.5                                                                   C-3 62.5 62.5                                                                 UV absorbing 2.0 2.0                                                          agent                                                                         γ-GPTMS  13.1 7.15                                                      γ-GPMDMS 10.0   9.71                                                    DBTDL 0.04                                                                    SH-6018 20.0 20.0 20.0 20.0                                                   Paint name CC20 CC21 CC22 CC23                                                Gelling 97 96 94 94                                                           coefficient (%)                                                               Initial gloss 20° 72 74 72 70                                          Pencil hardness HB F H F                                                      Gloss retention 89 84 60 66                                                   coefficient (%)                                                               Solvent ⊚ ⊚ ⊚ .circleincirc                                         le.                                        resistance                                                                  Resistance to                                                                            GOOD                                                                 acidity                                                                       Resistance to GOOD                                                            alkalinity                                                                  Secondary  100      100       100    100                                        adhesiveness                                                                  Resistance to 0.3 0.3 0.1 0.1                                                 yellowing due to                                                              heat (Δb)                                                               Resistance to ◯ ⊚ ◯ ◯      dirt shedding                                                               Critical wet film                                                                        329 μm or greater                                                 thickness in sag                                                              resistance test                                                               at vertical plane                                                           ______________________________________                                         Notes to Table 2:                                                             Numbers in the table indicate parts by weight.                                GPMDMS . . . abbreviation for glycidoxypropylmethyldimethoxysilane            SH6018 . . . abbreviation for Toray Silicone "SH6018", brand name of a        silicone compound produced by Toray Silicone Co., Ltd.                   

    Working         Comparative                                                                             Working   Working                                     example 24 example 2 example 3 example 4                                    ______________________________________                                        PAINT COMPOSITION                                                               A-3         100       100     188                                             C-3   62.5 250                                                                pigment 9.2 9.2                                                               disperser                                                                     R-930 21.6 21.6 53.8 53.8                                                     γ-GPTMS 5.0 3.8  14.3                                                   DBTDL  0.04                                                                   NMP 0.04 0.4 1.0 1.0                                                          TEXANOL 0.4 0.4 1.0 1.0                                                       10% TT-935 0.8                                                                Paint name CC24 CC'2 CC'3 CC'4                                              ______________________________________                                         Notes to Table 2:                                                             The numbers in the table are parts by weight.                                 (10% "TT935"): Resultant product when "PRIMAL TT935", the brand name of a     emulsion containing carboxylic acid groups manufactured by the U.S.           company Rohm & Haas Co., is neutralized with triethyl amine until the pH      is 8.2, and water is added to adjust the mixture so that the nonvolatile      content is 10%.                                                          

    Working        Comparative                                                                             Comparative                                                                             Comparative                                  example example example example                                               24 2 3 4                                                                    ______________________________________                                        PAINT SURFACE                                                                   PROPERTIES                                                                    Paint name  CC24     CC'2    CC'3    CC'4                                     Gelling 89 89 25 94                                                           coefficient (%)                                                               Initial gloss 20° 67 47 79 81                                          Pencil hardness 2B 2B 4B HB                                                   Gloss retention 62 72 3.8 3.8                                                 coefficient (%)                                                               Solvent ⊚ ⊚ X ⊚                  resistance                                                                    Resistance to GOOD GOOD blistering GOOD                                       acidity                                                                       Resistance to GOOD GOOD loss of GOOD                                          alkalinity   gloss and                                                           yellowing                                                                  Secondary 30 30 0 80                                                          adhesiveness                                                                  Resistance to 0.2 0.2 0.7 0.1                                                 yellowing due to                                                              heat (Δb)                                                               Critical wet film 329 μm or 152 μm 329 μm or 127 μm                                                     thickness in sag more  more                                                   resistance test                         at vertical plane                                                           ______________________________________                                                 Working   Comparative                                                                              Working                                           example 25 example 5 example 6                                              ______________________________________                                        PAINT COMPOSITION                                                               A-3          188         100                                                  C-3 62.5  250                                                                 pigment  9.2                                                                  disperser                                                                     aluminum paste 27.2 10.7 27.2                                                 γ-GPTMS 9.04 3.8 14.3                                                   DBTDL  0.04                                                                   NMP 1.0 0.4 1.0                                                               TEXANOL 1.0 0.4 1.0                                                           Paint name CC25 CC'5 CC'6                                                   ______________________________________                                         Notes to Table 2:                                                             Numbers in the table indicate parts by weight.                           

    Working            Comparative                                                                              Comparative                                       example example example                                                       25 5 6                                                                      ______________________________________                                        PAINT SURFACE                                                                   PROPERTIES                                                                    Paint name   CC25        CC'5     CC'6                                        Gelling 92 93 90                                                              coefficient (%)                                                               Pencil hardness F 2B F                                                        Solvent ⊚ ⊚ ⊚                    resistance                                                                  Resistance to                                                                            GOOD        GOOD                                                     acidity                                                                       Resistance to GOOD GOOD                                                       alkalinity                                                                  Secondary  70          30         80                                            adhesiveness                                                                  Resistance to 0.2 0.2 0.2                                                     yellowing due to                                                              heat (Δb)                                                               Metallic-like 200 185 130                                                     degrees IV value                                                            ______________________________________                                         Notes to Table 2                                                              Metalliclike degrees . . . IV value measured using "ALCOPE LMR100",           measuring apparatus of metalliclike degrees of film manufactured by Kansa     Paint Co., Ltd.                                                          

INDUSTRIAL APPLICABILITY

The present invention's curable resin composition for use in water-basedcoating materials which is obtained as above not only offers superiorcoating and curing properties, but also provides a cured coating whichhas excellent resistance to weathering, solvents, chemicals and water,even in the case where cured at ambient temperatures. Moreover, thiscomposition contains little or no organic solvent as compared toconventional products, therefore presenting no problem to theenvironment and reducing energy consumption when employed inmanufacturing and coating operations. Thus, this composition is highlybeneficial.

Accordingly, the present invention's curable resin composition for usein water-based coating materials can be used in a wide range ofapplications including use in such areas as automobile paint finishrepair, civil engineering, architectural and building projects, andgeneral applications, as well as applications on a variety of materialssuch as glass, plastic products and metallic materials like aluminum,stainless steel, chrome plating, hard pan, tin plate, and the like.

We claim:
 1. A curable resin composition for use in water-based coatingmaterials consisting essentially of, in combination,:an emulsion polymer(A), containing tertiary amino groups, obtained by carrying out emulsionpolymerization of a vinyl monomer containing a tertiary amino group withanother copolymerizable vinyl monomer in a water-based medium, and acompound (B) containing an epoxy group and a hydrolyzable silyl group,wherein the emulsion polymer (A) is obtained by means of a soap-freepolymerization method, and the emulsion polymer (A) is neutralized withan acidic compound at some point in the soap-free polymerization so thatthe ratio of the equivalent weight of the acidic compound to that ofamino groups in said emulsion polymer (A) containing tertiary aminogroups is 0.1 or more.
 2. A curable resin composition for use inwater-based coating materials comprising, in combination,:an emulsionpolymer (A), containing tertiary amino groups, obtained by carrying outemulsion polymerization of a vinyl monomer containing a tertiary aminogroup with another copolymerizable vinyl monomer in a water-basedmedium; a water-based compound (C) obtained by adding a neutralizingagent to a vinyl polymer (I) containing acidic groups and/or tertiaryamino groups so as to neutralize at least 10% of said acidic groupsand/or said tertiary amino groups, and then dispersing or dissolving inwater; and a compound (B) containing an epoxy group and a hydrolyzablesilyl group.
 3. A curable resin composition for use in water-basedcoating materials comprising, in combination,:an emulsion polymer (A),containing tertiary amino groups, obtained by carrying out emulsionpolymerization of a vinyl monomer containing a tertiary amino group withanother copolymerizable vinyl monomer in a water-based medium; acompound (B) containing an epoxy group and a hydrolyzable silyl group;and a compound (D), different from and in addition to compound (B),containing a hydrolyzable silyl group and/or silanol group.
 4. A curableresin composition for use in water-based coating materials comprising,in combination,:an emulsion polymer (A), containing tertiary aminogroups, obtained by carrying out emulsion polymerization of a vinylmonomer containing a tertiary amino group with another copolymerizablevinyl monomer in a water-based medium; a water-based compound (C)obtained by adding a neutralizing agent to a vinyl polymer (I)containing acidic groups and/or tertiary amino groups so as toneutralize at least 10% of said acidic groups and/or said tertiary aminogroups, and then dispersing or dissolving in water; a compound (B)containing an epoxy group and a hydrolyzable silyl group; and a compound(D), different from and in addition to compound (B), contains ahydrolyzable silyl group and/or silanol group.
 5. A curable resincomposition for use in water-base coating materials consistingessentially of, in combination:an emulsion polymer (A), containingtertiary amino groups, obtained by carrying out emulsion polymerizationof a vinyl monomer containing a tertiary amino group with anothercopolymerizable vinyl monomer in a water-based medium, and a compound(B) containing an epoxy group and a hydrolyzable silyl group, whereinthe emulsion polymer (A) is obtained by means of a soap-freepolymerization method, and the emulsion polymer (A) is neutralized witha basic compound at some point in the soap-free polymerization so that aratio of an equivalent weight of the basic compound to that of acidicgroups in said emulsion polymer (A) containing tertiary amino groups is0.1 or more.
 6. A curable resin composition for use in water-basedcoating materials according to one of claims 1 through 4 and 5, whereinthe emulsion polymer (A) containing tertiary amino groups also containscarboxyl groups.
 7. A curable resin composition for use in water-basedcoating materials according to one of claims 1 through 4 and 5, whereinthe emulsion polymer (A) containing tertiary amino groups is prepared byemploying at least a vinyl monomer containing a hydroxyl group as amonomer component thereof.
 8. A curable resin composition for use inwater-based coating materials according to one of claims 1 through 4 and5, wherein the emulsion polymer (A) containing tertiary amino groups isprepared by employing at least a vinyl monomer containing a cycloalkylgroup as a monomer component thereof.
 9. A curable resin composition foruse in water-based coating materials according to one of claims 1through 4, wherein the emulsion polymer (A), containing tertiary aminogroups, is obtained by means of a soap-free polymerization method usingan effective amount of emulsifying agent whereby improved waterresistance of the cured composition is achieved.
 10. A curable resincomposition for use in water-based coating materials according to one ofclaims 2 through 4, wherein an emulsion polymer (A) containing tertiaryamino groups is neutralized with an acidic compound so that the ratio ofthe equivalent weight of the acidic compound to that of amino groups insaid emulsion polymer (A) containing tertiary amino groups is 0.1 ormore.
 11. A curable resin composition for use in water-based coatingmaterials according to one of claims 2 through 4, wherein the emulsionpolymer ( A) containing tertiary amino groups is neutralized with abasic compound so that a ratio of an equivalent weight of the basiccompound to that of acidic groups in said emulsion polymer (A)containing tertiary amino groups is 0.1 or more.
 12. A curable resincomposition for use in water-based coating materials according to one ofclaims 1 through 4 and 5, wherein an emulsion polymer (A) containingtertiary amino groups is an acrylic polymer.
 13. A curable resincomposition for use in water-based coating materials according to one ofclaims 2 or 4, wherein the vinyl polymer (I) containing acidic groupsand/or tertiary amino groups is prepared using at least a vinyl monomercontaining a hydroxyl group as a starting component.
 14. A curable resincomposition for use in water-based coating materials according to one ofclaims 2 or 4, wherein the vinyl polymer (I) containing acidic groupsand/or tertiary amino groups is prepared using at least a vinyl monomercontaining a cycloalkyl group as a starting component.
 15. A curableresin composition for use in water-based coating materials according toone of claims 2 or 4, wherein the vinyl polymer (I), containing acidicgroups and/or tertiary amino groups, comprises, in combination, anacrylic polymer and a fluoro olefin polymer.
 16. A curable resincomposition for use in water-based coating materials according to one ofclaims 2 or 4, wherein the vinyl polymer (I), containing acidic groupsand/or tertiary amino groups, is a member selected from the groupconsisting of an acrylic polymer and a fluoro olefin polymer.